Actinic Radiation Curable Polymeric Mixtures, Cured Polymeric Mixtures And Related Processes

ABSTRACT

The present disclosure is directed to actinic radiation curable polymeric mixtures, cured polymeric mixtures, tires and tire components made from the foregoing, and related processes.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.15/539,007 filed Jun. 22, 2017 and assigned U.S. Pat. No. 10,683,381,which is a national stage application of PCT Application No.PCT/US2015/066288 filed Dec. 17, 2015, which claims priority to and anyother benefit of U.S. Provisional Patent Application Ser. No. 62/142,271filed Apr. 2, 2015, and U.S. Provisional Patent Application Ser. No.62/096,120 filed Dec. 23, 2014, the entire disclosure of each of whichis incorporated by reference herein.

FIELD

The present application is directed to actinic radiation curablepolymeric mixtures, cured polymeric mixtures, tires and tire componentsmade from the foregoing, and related processes.

BACKGROUND

Additive manufacturing (which encompasses processes such as “3DPrinting”) is a process whereby a three-dimensional article ismanufactured (such as by printing) layer by layer from raw material.Certain additive manufacturing processes manufacture an article bybuilding up cross-sectional layers of the article as compared to otherso-called subtractive manufacturing processes which require that certainportions of a manufactured article be removed in order to produce thearticle in its final shape or form. While various additive manufacturingmethods have existed since the 1980s, certain of them have been focusedupon the use of various plastic polymers such as acrylonitrile butadienestyrene (ABS), polycarbonate (PC), high density polyethylene (HDPE), andhigh impact polystyrene (HIPS). Another type of additive manufacturingprocess is roll-to-roll UV-NL (UV-assisted nanoimprint lithography)which has been used to manufacture various devices including batteryseparators and organic electronics.

SUMMARY

The present disclosure is directed to actinic radiation curablepolymeric mixtures, cured polymeric mixtures, tires and tire componentsmade from the foregoing, and related processes.

In a first embodiment, an actinic radiation curable polymeric mixture isdisclosed. The mixture comprises: (a) a polyfunctionalized dienemonomer-containing polymer having the formula: [P][F]_(n) where Prepresents a diene polymer chain, F represents a functional group, n is2 to about 15, and each F can be the same or different; (b) optionally,a chain extender based upon F or reactive with F; (c) at least oneactinic radiation sensitive photoinitiator; (d) optionally, aphotosensitizer; and (e) a polyfunctional crosslinker reactive with F.

In a second embodiment, a cured polymeric mixture is disclosed. Thecured polymeric mixture comprises a crosslinked polyfunctionalized dienepolymer comprising a diene polymer chain backbone P, multiple functionalgroups F where each F is the same or different, and crosslinkagesbetween pairs of functional groups.

In a third embodiment, a process for producing a cured polymeric productis disclosed. The process comprises providing an additive manufacturingdevice comprising a source of actinic radiation, an exterior supportstructure, an interior tank capable of containing a liquid mixture, andan interior support structure; providing a liquid mixture comprising theactinic radiation curable polymeric mixture of the first embodiment tothe interior tank; repeatedly forming upon a support structure a layerfrom the liquid mixture; using actinic radiation to cure each layer;thereby producing a cured polymeric product.

In a fourth embodiment, a kit for producing an elastomeric cured productby additive printing is disclosed. The kit comprises at least twocartridges, wherein at least one cartridge comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; and a chain extender based upon F or reactive with F; and atleast a second cartridge comprises a chain extender based upon F orreactive with F; at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer; and optionally a crosslinkerreactive with F.

In a fifth embodiment, a tire comprising at least one componentcomprised of the cured polymeric mixture according to second embodimentor the actinic radiation curable polymeric mixture of the firstembodiment that has been cured is disclosed.

In a sixth embodiment, a rubber good comprising the cured polymericmixture according to second embodiment or the actinic radiation curablepolymeric mixture of the first embodiment that has been cured isdisclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows exemplary closed hollow voids in treads, in cut-awayprofile with the top being the road-contacting surface.

FIG. 2 shows exemplary overhung voids in treads, in cut-away profilewith the top being the road-contacting surface.

FIG. 3 shows exemplary undercut voids in treads, in cut-away profilewith the top being the road-contacting surface.

DETAILED DESCRIPTION

The present disclosure is directed to actinic radiation curablepolymeric mixtures, cured polymeric mixtures, tires and tire componentsmade from the foregoing, and related processes.

In a first embodiment, an actinic radiation curable polymeric mixture isdisclosed. The mixture comprises: (a) a polyfunctionalized dienemonomer-containing polymer having the formula: [P][F]_(n) where Prepresents a diene polymer chain, F represents a functional group, n is2 to about 15, and each F can be the same or different; (b) optionally,a chain extender based upon F or reactive with F; (c) at least oneactinic radiation sensitive photoinitiator; (d) optionally, aphotosensitizer; and (e) a polyfunctional crosslinker reactive with F.

In a second embodiment, a cured polymeric mixture is disclosed. Thecured polymeric mixture comprises a crosslinked polyfunctionalized dienepolymer comprising a diene polymer chain backbone P, multiple functionalgroups F where each F is the same or different, and crosslinkagesbetween pairs of functional groups.

In a third embodiment, a process for producing a cured polymeric productis disclosed. The process comprises providing an additive manufacturingdevice comprising a source of actinic radiation, an exterior supportstructure, an interior tank capable of containing a liquid mixture, andan interior support structure; providing a liquid mixture comprising theactinic radiation curable polymeric mixture of the first embodiment tothe interior tank; repeatedly forming upon a support structure a layerfrom the liquid mixture; using actinic radiation to cure each layer;thereby producing a cured polymeric product.

In a fourth embodiment, a kit for producing an elastomeric cured productby additive printing is disclosed. The kit comprises at least twocartridges, wherein at least one cartridge comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; and a chain extender based upon F or reactive with F; and atleast a second cartridge comprises a chain extender based upon F orreactive with F; at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer; and optionally a crosslinkerreactive with F.

In a fifth embodiment, a tire comprising at least one componentcomprised of the cured polymeric mixture according to second embodimentor the actinic radiation curable polymeric mixture of the firstembodiment that has been cured is disclosed.

In a sixth embodiment, a rubber good comprising the cured polymericmixture according to second embodiment or the actinic radiation curablepolymeric mixture of the first embodiment that has been cured isdisclosed.

Definitions

The terminology as set forth herein is for description of theembodiments only and should not be construed as limiting the inventionas a whole.

As used herein, the phrase “actinic radiation” refers to electromagneticradiation capable of producing photochemical reactions.

As used herein, the phrase “additive manufacturing” refers to theprocess of joining materials to make objects from 3D model data, usuallylayer upon layer, as opposed to subtractive manufacturing methodologies.

As used herein, the term “cartridge” refers to a container that isadapted for or configured for use in an additive manufacturing device.

As used herein, the phrase “chain extender” refers to amonofunctionalized hydrocarbon or hydrocarbon derivative containing afunctional group that reacts with a functional end group of the dienepolymer chain and adds to the polymer chain, thereby increasing itsmolecular weight.

As used herein, the phrase “polyfunctional crosslinker” refers to ahydrocarbon or hydrocarbon derivative containing two or more functionalgroups which are capable of undergoing a reaction to providecross-linking between two diene polymer chains or within a diene polymerchain.

As used herein, the term “hydrocarbon” refers to a compound consistingentirely of carbon and hydrogen atoms.

As used herein, the phrase “hydrocarbon derivative” refers to ahydrocarbon containing at least one heteroatom (e.g., N, O, S).

As used herein, the term “mer” or “mer unit” means that portion of apolymer derived from a single reactant molecule (e.g., ethylene mer hasthe general formula —CH2CH2-).

As used herein, the term “(meth)acrylate” encompasses both acrylate andmethacrylate.

As used herein, the term “photoinitiator” refers to a compound thatgenerates free radicals. The term “photoinitiator” is usedinterchangeably herein with the phrase “actinic radiation sensitivephotoinitiator.”

As used herein, the term “photosensitizer” refers to a light absorbingcompound used to enhance the reaction of a photoinitiator. Uponphotoexcitation, a photosensitizer leads to energy or electron transferto a photoinitiator.

As used herein, the term “polyfunctionalized” refers to more than onefunctionalization and includes polymers that have beendi-functionalized, tri-functionalized, etc. Generally, functionalizationof a polymer may occur at one or both ends of a polymer chain, along thebackbone of the polymer chain, in a side chain, and combinationsthereof.

As used herein, the term “polymer” refers to the polymerization productof two or more monomers and is inclusive of homo-, co-, ter-,tetra-polymers, etc. Unless indicated to the contrary herein, the termpolymer includes oligomers.

As used herein, the term “void” refers to a portion of a tire tread thatis devoid of material (other than air); the term can include grooves orchannels extending around all or a portion of the circumference of thetire as well as a pocket or cavity that does not extend around thecircumference of the tire.

Actinic Radiation Curable Polymeric Mixture

As discussed above, the first embodiment disclosed herein relates to anactinic radiation curable polymeric mixture comprising (a) apolyfunctionalized diene monomer-containing polymer having the formula:[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; (b) optionally a chain extender based upon F or reactive withF; (c) at least one actinic radiation sensitive photoinitiator; (d)optionally, a photosensitizer; and (e) a polyfunctional crosslinkerreactive with F. Generally, the actinic radiation curable polymericmixture is suitable for use in additive manufacturing processes whichutilize various additive manufacturing devices. The product or articleproduced by curing the actinic radiation curable polymeric mixture isreferred to herein as a cured elastomeric/polymeric product. In certainembodiments according to the first embodiment, the actinic radiationcurable polymeric mixture is curable by light having a wavelength in theUV to Visible range. In certain embodiments, the actinic radiation(light) has a wavelength of about 320 to less than 500 nm, includingabout 350 to about 450 nm, and about 365 to about 405 nm. Generally,there are two types of radiation induced curing chemistries: freeradical and cationic. Free radical curing involves cross-linking throughdouble bonds, most usually (meth)acrylate double bonds. Cationic curinginvolves cross-linking through other functional groups, most usuallyepoxy groups.

Polyfunctionalized Diene Monomer-Containing Polymer

As discussed above, the actinic radiation curable polymeric mixturecomprises a polyfunctionalized diene monomer-containing polymer whichcomprises a diene polymer chain [P]. In certain embodiments, the actinicradiation curable polymeric mixture comprises one type ofpolyfunctionalized diene monomer-containing polymer and in otherembodiments, the mixture comprises more than one type ofpolyfunctionalized diene monomer-containing polymer. Polyfunctionalizeddiene monomer-containing polymers can be categorized into differenttypes based upon one or more of: molecular weight, monomer type(s),relative amount of monomer(s), types of functional group(s) (e.g., freeradical polymerizable or cationic polymerizable), identity of functionalgroup(s) (as discussed in more detail below), and amount of functionalgroup(s). In certain embodiments, the polyfunctionalized dienemonomer-containing polymer(s) can be referred to as a pre-polymer sincethey will react with each other and with a chain extender (when a chainextender is present) to form a higher molecular weight polymer. Thediene polymer chain comprises (is based upon) at least one dienemonomer. A diene monomer is a monomer having two carbon-carbon doublebonds. Various diene monomers exist and are generally suitable for usein preparing the diene polymer chain of the polyfunctionalized dienemonomer-containing polymer. In certain embodiments according to thefirst-fifth embodiments disclosed herein, the diene polymer chain of thepolyfunctionalized diene monomer-containing polymer comprises monomersselected from at least one of: acyclic and cyclic dienes having 3 toabout 15 carbon atoms. In certain embodiments according to thefirst-fifth embodiments disclosed herein, the diene polymer chain of thepolyfunctionalized diene monomer-containing polymer comprises monomersselected from at least one of: 1,3-butadiene, isoprene, 1,3-pentadiene,1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene,farnescene, and substituted derivatives of each of the foregoing. Incertain embodiments, the diene polymer chain of the polyfunctionalizeddiene monomer-containing polymer comprises 1,3-butadiene monomer,isoprene monomer, or a combination thereof. In certain embodiments, thediene polymer chain of the polyfunctionalized diene-monomer-containingpolymer further comprises at least one vinyl aromatic monomer.Non-limiting examples of suitable vinyl aromatic monomers include, butare not limited to, styrene, α-methyl styrene, p-methylstyrene,o-methylstyrene, p-butylstyrene, vinylnaphthalene, p-tertbutylstyrene,vinyl catechol-based, and combinations thereof. In certain embodiments,the diene polymer chain of the polyfunctionalized dienemonomer-containing polymer comprises a combination of 1,3-butadienemonomer and styrene monomer.

As discussed above, the term “polyfunctionalized” is used herein torefer to more than one functionalization and includes polymers that havebeen di-functionalized, tri-functionalized, etc. Generally,functionalization of a polymer may occur at one or both ends of apolymer chain, along the backbone of the polymer chain, and combinationsthereof. Generally, each F functional group present in thepolyfunctionalized diene monomer-containing polymer may be same ordifferent. In certain embodiments according to the first-fifthembodiments disclosed herein, the polyfunctionalized dienemonomer-containing polymer comprises a di-functionalized polymer havingan F functional group at each terminal end of the polymer chain; each Ffunctional group may be the same or different. In certain embodimentsaccording to the first-fifth embodiments disclosed herein, thepolyfunctionalized diene monomer-containing polymer comprises adi-functionalized polymer having a F functional group at one terminalend of the polymer chain and at least one additional F functional groupalong the backbone of the polymer chain; each F functional group may bethe same or different. In certain embodiments according to thefirst-fifth embodiments disclosed herein, the polyfunctionalized dienemonomer-containing polymer comprises a functionalized polymer having atleast three F functional groups, with one at each terminal end of thepolymer chain, and at least one along the backbone of the polymer chain;each F functional group may be the same or different.

Various polyfunctionalized diene monomer-containing polymers arecommercially available and may be suitable for use in variousembodiments of the first-fifth embodiments disclosed herein.Non-limiting examples of these include, but are not limited to, SartomerCN307 polybutadiene dimethacrylate, Sartomer CN301 polybutadienedimethacrylate and Sartomer CN303 hydrophobic acrylate ester, allavailable from Sartomer Americas (Exton, Pa.); Ricacryl® 3500methacrylated polybutadiene, Ricacryl® 3801 methacrylated polybutadiene,Ricacryl® 3100 methacrylated polybutadiene, all available from CrayValley USA LLC (Exton, Pa.); BAC-45 polybutadiene diacrylate and BAC-15polybutadiene diacrylate, available from San Esters Corp. (New York,N.Y.); Kuraray UC-102 methacrylated polyisoprene and UC-203methacrylated polyisoprene, available from Kuraray America Inc.(Pasadena, Tex.); Poly bd® 600E epoxidized polybutadiene and Poly bd®605E polybutadiene, available from Cray Valley USA LLC (Exton, Pa.).Methods for preparing polyfunctionalized diene monomer-containingpolymers are well-known to those of skill in the art and include thoseusing functional initiators, functional terminators and reactions ofdiol terminated dienes with various functional acid chlorides or withcarboxylic acids (through a dehydration reaction). Other methods includethe reaction of an oxidant and a carboxylic acid to form a peracid foradding an epoxy group.

In certain embodiments, the diene polymer chain of thepolyfunctionalized diene monomer-containing polymer comprises:polybutadiene, styrene-butadiene copolymer, polyisoprene,ethylene-propylene-diene rubber (EPDM), styrene-isoprene rubber, orbutyl rubber (halogenated or non-halogenated).

The molecular weight of the polyfunctionalized diene monomer-containingpolymer may vary widely depending upon various factors, including, butnot limited to the amount and type of chain extender (if any) that isutilized in the actinic radiation curable polymeric mixture. Generally,higher molecular weight polymers will lead to better properties in thecured article or product, but will also lead to higher viscosities inthe overall actinic radiation curable polymeric mixture. Thus, preferredpolyfunctionalized diene monomer-containing polymers for use in themixture will balance molecular weight with its effect on viscosity. Incertain embodiments, the polyfunctionalized diene monomer-containingpolymer has a Mn of about 3,000 to about 135,000 grams/mole (polystyrenestandard). In certain embodiments, the polyfunctionalized dienemonomer-containing polymer has a Mn of 3,000 to 135,000 grams/mole(polystyrene standard); including about 5,000 to about 100,000grams/mole (polystyrene standard); 5,000 to 100,000 grams/mole(polystyrene standard); about 10,000 to about 75,000 grams/mole(polystyrene standard); and 10,000 to 75,000 grams/mole (polystyrenestandard). The number average molecular weights (M) values that arediscussed herein for the polyfunctionalized diene monomer-containingpolymer include the weight contributed by the functional groups (F).

In certain embodiments, the cured elastomeric mixture comprisescrosslinked polyfunctionalized diene monomer-containing polymer has a Mc(molecular weight between crosslinks) of about 500 to about 150,000grams/mole, including 500 to 150,000 grams/mole (e.g., 1000, 2500, 5000,10000, 20000, 25000, 30000, 40000, 50000, 60000, 70000, 80000, 90000,100000, 110000, 115000, 120000, 130000, 140000 or 150000). Thecrosslinked molecular weight (M_(c)) values that are discussed hereinfor the polyfunctionalized diene monomer-containing polymer include theweight contributed by the functional groups (F). M_(c) can be determinedin accordance with previously published procedures such as thosedisclosed in Hergenrother, J., Appl. Polym. Sci., v. 32, pp. 3039(1986), herein incorporated by reference in its entirety.

In certain embodiments, the molecular weight of the crosslinkedpolyfunctionalized diene monomer-containing polymer of the curedelastomeric mixture can be quantified in terms of M_(r) or molecularweight between chain restrictions. In certain embodiments, the curedelastomeric mixture comprises crosslinked polyfunctionalized dienemonomer-containing polymer has a Mc (molecular weight betweencrosslinks) of about 500 to about 150,000 grams/mole, including 500 to150,000 grams/mole (e.g., 1000, 2500, 5000, 10000, 20000, 25000, 30000,40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 115000,120000, 130000, 140000 or 150000). The crosslinked molecular weight(M_(c)) values that are discussed herein for the polyfunctionalizeddiene monomer-containing polymer include the weight contributed by thefunctional groups (F). Generally M_(r) can be determined according tothe procedure described in U.S. Patent Application Publication No.2012/0174661, herein incorporated by reference in its entirely. Morespecifically, M_(r) can be determined according to the followingequation:

$M_{r} = \frac{\rho \; {{RT}\left( {\Lambda - \Lambda^{- 2}} \right)}}{\sigma}$

where ρ is the compound density, σ is stress, R is the gas constant, Tis temperature, Λ is 1+Xϵ where X is the strain amplification factorfrom the Guth-Gold equation and the strain (ϵ) is (1−1_(set))/1_(set)where 1 is the specimen length at a point on the retraction curve and1_(set) is the specimen length after retraction to zero stress. A TR ortensile retraction test set consists of at least two tensile retractiontests, each to a progressively higher target extension ratio, Λmax,followed immediately by a retraction to a zero stress. Each tensile pulland subsequent retraction are performed at the same testing rate suchthat a series of extension and retraction curve pairs are obtained.During each retraction, the stress, σ, is measured as a function ofextension ratio, Λ, defining the tensile retraction curve. Testing maybe performed in accordance with the procedures outlined in Hergenrother,J., Appl. Polym. Sci., v. 32, pp. 3039 (1986), herein incorporated byreference in its entirety.

When determining M_(r) for compounds containing rigid fillers, theenhancement of modulus due to rigid particles should be taken intoaccount in a fashion similar to that of Harwood and Payne, J. Appl.Polym. Sci., v. 10, pp. 315 (1966) and Harwood, Mullins and Payne, J.Appl. Polym. Sci, v. 9, pp. 3011 (1965), both of which are hereinincorporated by reference in their entirety. When a filled compound isfirst stretched in tension to the same stress as its corresponding gumcompound (e.g., non-filled compound), subsequent retraction andextension curves are generally very similar to those of the gumcompounds when stress is graphed as a function of normalized strain.Normalized strain is defined as the strain at any point on thesubsequent extension or retraction curves divided by the maximum strainof the initial extension. For retraction curves in particular, and formaximum strains of natural rubber gum compounds up to and including nearbreaking strain, this could be applied to a number of filled compounds.The result can be interpreted as evidence of strain amplification of thepolymer matrix by the filler, where the average strain the polymermatrix of a filled compound is the same as that in the corresponding gum(non-filled) compound, when the filled and gum compounds are compared atthe same stress. Strain amplification X can be determined by theGuth-Gold equation as discussed in Mullins et al., J.Appl. Polym. Sci.,vol. 9, pp. 2993 (1965) and Guth et al., Phys. Rev. v. 53, pp. 322(1938), both of which are herein incorporated by reference in theirentirety. After correction of A for filler level, neo-Hookean rubberelasticity theory (Shen, Science & Technology of Rubber, Academic Press,New York, 1978, pp. 162-165, herein incorporated by reference) may beapplied to an internal segment of the retraction curve from which amolecular weight between chain restrictions of all types, M_(r) can becalculated according to the above equation. Extension of the same rubberspecimen to successively higher Λmax provides M_(r) as a function ofΛmax.

Tensile retraction testing can be measured using a special ribbed TRmold to prevent slippage when stretched in tension between clamps of anInstron 1122 tester controlled by a computer (for testing, dataacquisition and calculations), as described in Hergenrother, J., Appl.Polym. Sci., v. 32, pp. 3039 (1986). Specimens for testing may benominally 12 mm wide by 50 mm long by 1.8 mm thick. M_(r) can becalculated at each of 25 (σ, Λ) pairs, collected from about the middleone-third of the particular retraction curve. M_(r) values as disclosedherein may be the average of the 25 calculated values. In order toreduce test time, elongations to successively higher Λmax can be carriedout at successively higher speeds of the Instron crosshead motion. Amaster TR curve can be obtained by shifting the different test speeds toa standardized testing rate of 5%/minute. High strain (greater thanabout 40% to 80% elongation) region of the smooth curve obtained may befitted by a linear equation of the form of M_(r)=S(Λmax−1)+Mc. The fitto strain region at less than 80% elongation may deviate steadily fromthe M_(r) line as strains are progressively reduced. The logarithim ofsuch difference between the calculated and observed ve can be plottedversus the lower level of strain to give a linear fit to Λve as afunction of (Λmax−1). The antilog of the reciprocal of the intercept, m,can be denoted as B (expressed in kg/mole) and relates to themicro-dispersion of the filler. See, U.S. Pat. No. 6,384,117, hereinincorporated by reference in its entirety. In a similar fashion, thelowest strain deviation can be treated to give a plot of ΛΛve as afunction of (Λmax−1). The antilog of the reciprocal of the intercept forthe process that occurs at strains of less than 6% elongation can bedenoted as y (expressed in kg/mole). These three equations, each with aslope and intercept, can be used to fit the various strain regions ofthe TR curve can be summed to provide a single master equation thatempirically describes the M_(r) response over the entire range oftesting. Experimental constants of the new master equation can beadjusted using ExcelSolver® to obtain the best possible fit of thepredicted values to the experimental values obtained by TR. Fittingcriteria consisting of a slope and an intercept can be determined whenthe experimental and curve fit values of M_(r) are compared. Thecomposite equation can allow the transition between each fitted linearregion to be independent of the choice of the experimental strainsmeasured and the small mathematical adjusting of the strain range canallow a more precise linear fit of the data to be made.

F Functional Groups

As discussed above, F represents a functional group associated with thepolyfunctionalized diene monomer-containing polymer. Various types offunctional groups F may be suitable for use in certain embodiments ofthe first-fifth embodiments disclosed herein. In certain embodiments,these functional groups F can be described as either free radicalpolymerizable or cationic polymerizable, which is a general descriptionof how the groups react upon exposure to actinic radiation (light) toresult in cross-linking or curing. Generally, functional groups thatimprove curability (cross-linking) by actinic radiation are useful asthe functional group F.

In certain embodiments, the F functional group of the polyfunctionalizeddiene monomer-containing polymer comprises a free radical polymerizablefunctionalizing group. In certain embodiments, the F functional group ofthe polyfunctionalized diene monomer-containing polymer comprises acationic polymerizable functionalizing group. In certain embodiments,the F functional group of the polyfunctionalized dienemonomer-containing polymer comprises a combination of cationicpolymerizable and free radical polymerizable functional groups either onthe same diene polymer chain or on separate diene polymer chains.Generally, functional groups that are free radical polymerizable havethe advantage of reacting faster than cationic polymerizablefunctionalizing groups, but the disadvantage is being prone toinhibition by oxygen exposure. Generally, functional groups that arecationic polymerizable have the advantage of being resistant to oxygenexposure (i.e., they are not inhibited), but have the disadvantages ofbeing prone to inhibition by water exposure and having a generallyslower rate of reaction. The combination of cationic polymerizable andfree radical polymerizable functional groups can be advantageous asproviding the advantages of each type and minimizing the disadvantagesof each alone; an additional advantage of such a combination is to allowfor a double network system wherein a crosslink of a first type occursat a first wavelength and a crosslink of a second type occurs at asecond wavelength or a single wavelength is used to activate both typesof photoinitators which will create a double network.

In certain embodiments, each functional group F in thepolyfunctionalized diene monomer-containing polymer comprises at leastone of: acrylate, methacrylate, cyanoacrylate, epoxide, aziridine, andthioepoxide. In certain embodiments, each functional group F in thepolyfunctionalized diene monomer-containing polymer comprises anacrylate or methacrylate. Suitable acrylates or methacrylates may belinear, branched, cyclic, or aromatic. As used herein, the term acrylateshould be understood to include both acrylic acid and esters thereof.Similarly, the term methacrylate should be understood to include bothmethacrylic acid and esters thereof. Various types of acrylates andmethacrylates are commonly used and may be suitable for use as thefunctional group F. In certain embodiments of the first-fifthembodiments disclosed herein, the function group F comprises at leastone of: acrylic acid, methacrylic acid, ethyl (meth)acrylate, methyl(meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,cyclobutyl (meth)acrylate, (cyano)acrylate, 2-ethylhexyl(meth)acrylate,isostearyl (meth)acrylate, isobornyl (meth)acrylate, propyl(meth)acrylate, isopropyl (meth)acrylate, cyclopropyl (meth)acrylate,pentyl (meth)acrylate, isopentyl (meth)acrylate, cyclopentyl(meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate,cyclohexyl (meth)acrylate, heptyl (meth)acrylate, isoheptyl(meth)acrylate, cycloheptyl (meth)acrylate, octyl (meth)acrylate,cyclooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl(meth)acrylate, cyclononyl (meth)acrylate, decyl (meth)acrylate,isodecyl (meth)acrylate, cyclodecyl (meth)acrylate, undecyl(meth)acrylate, isoundecyl (meth)acrylate, cycloundecyl (meth)acrylate,lauryl (meth)acrylate, tridecyl (meth)acrylate, isotridecyl(meth)acrylate, cyclotridecyl (meth)acrylate, tetradecyl (meth)acrylate,isotetradecyl (meth)acrylate, cyclotetradecyl (meth)acrylate, pentadecyl(meth)acrylate), isopentadecyl (meth)acrylate, cyclopentadecyl(meth)acrylate, and combinations thereof. In certain embodiments, eachfunctional group F in the polyfunctionalized diene monomer-containingpolymer comprises an epoxide or a thioepoxide. In certain embodiments,each functional group F in the polyfunctionalized dienemonomer-containing polymer comprises an aziridine, which generally canbe considered to be a compound containing the aziridine functional group(a 3-membered heterocyclic group with one amine (—NR—), where R is H,CH₃, and two methylenes (—CH₂—).

In certain embodiments, the chain extender may be chosen based uponcompound having a moiety that is reactive with the F functional group ofthe polyfunctionalized diene monomer-containing polymer.

In certain embodiments, the chain extender comprises one or moreadditional functional groups F1 along the backbone of the polymer. Suchfunctional groups may be chosen based upon their contribution todesirable properties in the cured polymeric mixture, the curedelastomeric 3-dimensional article or final product. As a non-limitingexample, the F1 functional groups may be selected to interact with oneor more fillers such as silica filler, i.e., F1 comprises asilica-reactive functional group. Thus, in certain embodiments thepolyfunctionalized diene monomer-containing polymer comprises at leastone F1 silica-reactive functional group along its backbone. Non-limitingexamples of silica-reactive functional groups includenitrogen-containing functional groups, silicon-containing functionalgroups, oxygen- or sulfur-containing functional groups, andmetal-containing functional groups. Another specific example of a F1functional group includes phosphorous-containing functional groups.

Non-limiting examples of nitrogen-containing functional groups that canbe utilized as a F1 silica-reactive functional group along the backboneof the polyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, any of a substituted orunsubstituted amino group, an amide residue, an isocyanate group, animidazolyl group, an indolyl group, a nitrile group, a pyridyl group,and a ketimine group. The foregoing substituted or unsubstituted aminogroup should be understood to include a primary alkylamine, a secondaryalkylamine, or a cyclic amine, and an amino group derived from asubstituted or unsubstituted imine. In certain embodiments of thefirst-third embodiments, the polyfunctionalized diene monomer-containingpolymer comprises at least one F1 functional group along its backboneselected from the foregoing list of nitrogen-containing functionalgroups.

Non-limiting examples of silicon-containing functional groups that canbe utilized as a F1 silica-reactive functional group along the backboneof the polyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, an organic silyl or siloxygroup, and more precisely, the functional group may be selected from analkoxysilyl group, an alkylhalosilyl group, a siloxy group, analkylaminosilyl group, and an alkoxyhalosilyl group. Suitablesilicon-containing functional groups for use in functionalizingdiene-based elastomer also include those disclosed in U.S. Pat. No.6,369,167, the entire disclosure of which is herein incorporated byreference. In certain embodiments of the first-third embodiments, thepolyfunctionalized diene monomer-containing polymer comprises at leastone F1 functional group along its backbone selected from the foregoinglist of silicon-containing functional groups.

Non-limiting examples of oxygen- or sulfur-containing functional groupsthat can be utilized as a F1 silica-reactive functional group along thebackbone of the polyfunctionalized diene monomer-containing polymer incertain embodiments include, but are not limited to, a hydroxyl group, acarboxyl group, an epoxy group, a glycidoxy group, a diglycidylaminogroup, a cyclic dithiane-derived functional group, an ester group, analdehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, athioepoxy group, a thioglycidoxy group, a thiodiglycidylamino group, athioester group, a thioaldehyde group, a thioalkoxy group, and athioketone group. In certain embodiments, the foregoing alkoxy group maybe an alcohol-derived alkoxy group derived from a benzophenone. Incertain embodiments of the first-third embodiments, thepolyfunctionalized diene monomer-containing polymer comprises at leastone F1 functional group along its backbone selected from the foregoinglist of oxygen- or sulfur-containing functional groups.

Non-limiting examples of phosphorous-containing functional groups thatcan be utilized as a F1 functional group along the backbone of thepolyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, organophosphorous compounds(i.e., compounds containing carbon-phosphorous bond(s)) as well asphosphate esters and amides and phosphonates. Non-limiting examples oforganophosphorous compounds include phosphines including alkylphosphines and aryl phosphines. In certain embodiments of thefirst-third embodiments, the polyfunctionalized diene monomer-containingpolymer comprises at least one F1 functional group along its backboneselected from the foregoing list of phosphorous-containing functionalgroups.

Chain Extender

As discussed above, the actinic radiation curable polymeric mixtureoptionally comprises a chain extender based upon F or reactive with F.In other words, in certain embodiments the mixture comprises a chainextender, but it is not considered to be essential in all embodiments.Generally, the chain extender is a hydrocarbon or hydrocarbon derivativethat is monofunctionalized with a functional group that reacts with afunctional end group of the dienepolymer chain of the polyfunctionalizeddiene monomer-containing polymer and is used to increase the molecularweight of the polyfunctionalized diene monomer-containing polymer (bybonding to one of the F groups of the polymer). Preferably, the chainextender lowers the viscosity of the overall actinic radiation curablepolymeric mixture and also acts to increase the molecular weight of thepolyfunctionalized diene monomer-containing polymer between crosslinks.In certain embodiments, the chain extender also increases the elongationat break of the cured elastomeric/polymeric mixture that results fromactinic radiation curing the polymeric mixture.

In certain embodiments when the chain extender is present, it comprisesa compound that is based upon F. In other words, such a chain extendercompound comprises an F group. In certain embodiments when the chainextender is present, it comprises a compound that is based upon F or acompound that is reactive with F. By reactive with F is meant a compoundcontaining a moiety that will bond with the F group of thepolyfunctionalized diene monomer-containing polymer.

As discussed above, in those embodiments where the chain extender ispresent, it may comprise a hydrocarbon or hydrocarbon derivative withmonofunctionality selected from various functional groups either basedon F or reactive with F. In certain embodiments when the chain extenderis present, it is selected so that the Tg of the chain-extendedpolyfunctionalized diene monomer-containing polymer is less than about25° C., including about −65° C. to about 10° C. Preferably, the chainextender is selected so that the Tg of the extended polyfunctionalizeddiene monomer-containing polymer even after crosslinking is less thanabout 25° C., including about −65° C. to about 10° C. In certainembodiments when the chain extender is present, it comprises a compoundthat has a Mw of about 72 to about 1000 grams/mole, including about 72to about 500 grams/mole.

In certain embodiments of the first-fifth embodiments, when the chainextender is present, it comprises at least one alkyl (meth)acrylatemonomer. In certain such embodiments, the alky (meth)acrylate monomer iscomprised of an alkyl chain selected from C2 to about C18 and having areactive meth(acrylate) head group, termed alkyl functionalized(meth)acrylates; alkyl (meth)acrylate monomers having larger alkylgroups may have a thermal transition, Tm, that is higher than desired.By utilizing as a chain extender a compound/monomer that contains onlyone functional group (e.g., a (meth)acrylate) it is possible to increasethe molecular weight between crosslinks, while reducing the viscosity.

In certain embodiments when the F group of the polyfunctionalized dienemonomer-containing polymer comprises an acrylate or methacrylate, thechain extender comprises at least one alkyl (meth)acrylate monomer. Incertain such embodiments, the alky (meth)acrylate monomer is at leastone monomer selected from C2 to about C18 alkyl functionalized(meth)acrylates; alkyl (meth)acrylate monomers having larger alkylgroups may have a Tg that is higher than desired and may unduly increasethe Tg of the overall actinic radiation curable polymeric mixture.

In certain embodiments, the total amount of polyfunctionalized dienemonomer-containing polymer and chain extender can be considered to be100 parts by weight; in certain such embodiments, the polyfunctionalizeddiene monomer-containing polymer is present in an amount of 1-100 partsby weight and the chain extender is present in an amount of 0-99 partsby weight. In other words, the chain extender is optional in certainembodiments. Generally, the relative amounts of polyfunctionalized dienemonomer-containing polymer and chain extender can vary greatly because,as discussed above, upon exposure to actinic radiation the chainextender adds to the polymer and increases its molecular weight. As anon-limiting example, when the Mn of the polyfunctionalized dienemonomer-containing polymer is relatively low (e.g., about 3,000grams/mole, polystyrene standard), and the Mw of the chain extender isrelatively high (e.g., about 1000 grams/mole), the total amount ofpolyfunctionalized diene monomer-containing polymer and chain extendercan comprise relatively less polymer than chain extender. In certainembodiments, the polyfunctionalized diene monomer-containing polymer ispresent in an amount of 1-90 parts by weight and the chain extender ispresent in an amount of 10-99 parts by weight, including 1-80 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 20-99 parts by weight, 1-70 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 30-99 parts by weight, 1-60 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 40-99 parts by weight, 1-50 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 50-99 parts by weight, 1-40 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 60-99 parts by weight, 1-30 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 70-99 parts by weight, 1-20 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 80-99 parts by weight, 1-10 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 10-99 parts by weight. In certainembodiments, the polyfunctionalized diene monomer-containing polymer ispresent in an amount of 10-99 parts by weight and the chain extender ispresent in an amount of 1-90 parts by weight, including 20-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-80 parts by weight, 30-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-70 parts by weight, 40-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-60 parts by weight, 50-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-50 parts by weight, 60-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-40 parts by weight, 70-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-30 parts by weight, 80-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-20 parts by weight, 90-99 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 1-10 parts by weight.

In certain embodiments, when the F groups of the polyfunctionalizeddiene monomer-containing polymer comprise (meth)acrylate and the Fgroups of the chain extender comprise an alkyl (meth)acrylate, therelative amounts of polymer and chain extender are about 50 parts and 50parts, respectively, including about 40 to about 60 parts polymer andabout 60 to about 40 parts chain extender; 40 to 60 parts polymer and 60to 40 parts chain extender; about 45 to about 60 parts polymer and about55 to about 40 parts chain extender; 45 to 60 parts polymer and 55 to 40parts chain extender; about 50 to about 60 parts polymer and about 40 toabout 50 parts chain extender; 50 to 60 parts polymer and 40 to 50 partschain extender; about 55 to about 60 parts polymer and about 40 to about45 parts chain extender; and 55 to 60 parts polymer and 40 to 45 partschain extender.

In certain embodiments, in addition to being monofunctionalized with atleast one F group or a functional group reactive with F, the chainextender is further functionalized with at least one functional group F2that is molecular oxygen reactive. Non-limiting examples of suitable F2groups include various amines, including, but not limited to, tertiaryamines, secondary amines, and primary amines; thiols; silanes;phosphites, tin-containing compounds, lead containing compounds, andgermanium-containing compounds. Incorporating at least one molecularoxygen reactive F2 functional group into the chain extender reduces theamount of undesirable oxidation that may otherwise occur from eithersolubilized oxygen within the actinic radiation curable polymericmixture or atmospheric oxygen. Without being bound by theory, afunctional group F2 that is molecular oxygen reactive can react with anyperoxy radicals that are generated (e.g., from the reaction of a freeradical with molecular oxygen) to create a new initiator by hydrogenabsorption; this reaction avoid or minimizes the undesirable reactionbetween a peroxy radical and an initiator (which will yield anon-productive product and consume the initiator). The amount of F2functionalization on the chain extender may vary. In certainembodiments, the chain extender is about 10 to 100% functionalized withat least one functional group F2 that is molecular oxygen reactive,including 10 to 100% functionalized, about 20 to 100% functionalized, 20to 100% functionalized, about 30 to 100% functionalized, 30 to 100%functionalized, about 40 to 100% functionalized, 40 to 100%functionalized, about 50 to 100% functionalized, 50 to 100%functionalized, about 10 to about 90% functionalized, 10 to 90%functionalized, about 10 to about 80% functionalized, 10 to 80%functionalized, about 10 to about 70% functionalized, 10 to 70%functionalized, about 10 to about 60% functionalized, 10 to 60%functionalized, about 10 to about 50% functionalized, and 10 to 50%functionalized. In other embodiments, in addition to comprising at leastone functional group F2 that is molecular oxygen reactive or as analternative to comprising at least one functional group F2 that ismolecular oxygen reactive, a separate molecular oxygen reactiveingredient can be utilized in the actinic radiation curable polymericmixture. Generally, this separate ingredient comprises a hydrocarbon orhydrocarbon derivative functionalized with at least one of thefunctional groups discussed above for F2.

Photoinitiator

As discussed above, the actinic radiation curable polymeric mixturecomprises at least one actinic radiation sensitive photoinitiator. Incertain embodiments, the polymeric mixture comprises two, three, or moreone actinic radiation sensitive photoinitiators. Generally, the purposeof the photoinitiator is to absorb actinic radiation (light) andgenerate free radicals or a Lewis acid that will react with thefunctional groups of the polymer resulting in polymerization. Two typesof actinic radiation sensitive photoinitators exist: free radical andcationic. Free radical photoinitiators can themselves be separated intotwo categories, those that undergo cleavage upon irradiation to generatetwo free radicals (e.g., benzoins, benzoin ethers, and alpha-hydroxyketones) and those that form an excited state upon irradiation and thenabstract an atom or electron from a donor molecule which itself thenacts as the initiating species for polymerization (e.g., benzophenones).In certain embodiments of the first-fifth embodiments disclosed herein,the photoinitiator comprises at least one free radical photoinitiator.In certain embodiments of the first-fifth embodiments disclosed herein,the photoinitiator comprises at least one cationic photoinitiator. Incertain embodiments of the first-fifth embodiments disclosed herein, thephotoinitiator comprises a combination of at least one free radicalphotoinitiator and at least one cationic photoinitiator.

When a photoinitiator is utilized, various photoinitiators are suitablefor use in the actinic radiation curable polymeric mixtures. In certainembodiments of the first-fifth embodiments disclosed herein, thephotoinitiator comprises at least one of: a benzoin, an aryl ketone, analpha-amino ketone, a mono- or bis(acyl)phosphine oxide, a benzoin alkylether, a benzil ketal, a phenylglyoxalic ester or derivatives thereof,an oxime ester, a per-ester, a ketosulfone, a phenylglyoxylate, aborate, and a metallocene. In certain embodiments of the first-fifthembodiments disclosed herein, the photoinitiator comprises at least oneof: a benzophenone, an aromatic α-hydroxyketone, a benzilketal, anaromatic α-aminoketone, a phenylglyoxalic acid ester, amono-acylphosphinoxide, a bis-acylphosphinoxide, and atris-acylphosphinoxide. In certain embodiments of the first-fifthembodiments disclosed herein, the photoinitiator is selected frombenzophenone, benzildimethylketal, 1-hydroxy-cyclohexyl-phenyl-ketone,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-lone,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one,(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,(4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane,(2,4,6-trimethylbenzoyl)diphenylphosphine oxide,bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propan-1-one,1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime),oligo[2-hydroxy-2-methyl-1-[4-methylvinyl]phenyl]propanone,2-hydroxy-2-methyl-1-phenyl propan-1-one, and combinations thereof.

The amount of actinic radiation sensitive photoinitiator(s) utilized canvary. In certain embodiments of the first-fifth embodiments disclosedherein, when the photoinitiator is present, the actinic radiationcurable polymeric mixture comprises about 1 to about 10 parts by weightof the photoinitiator, including about 2 to about 5 parts by weight (allamounts based upon 100 total parts of polyfunctionalized dienemonomer-containing polymer and chain extender). The foregoing amountsshould be understood to apply to both free radical and cationicphotoinitiators and to refer to the total amounts (by weight) of allphotoinitiators used in the actinic radiation curable polymeric mixture.

Photosensitizer

As discussed above, in certain embodiments, the actinic radiationcurable polymeric mixture comprises a photosensitizer. In other words,in certain embodiments, the photosensitizer is optional. Generally, the“photosensitizer” is a light absorbing compound used to enhance thereaction of a photoinitiator; it may absorb part of the actinicradiation (light) that the photoinitiator cannot absorb and transfer theenergy to the photoinitiator. Upon photoexcitation, a photosensitizerleads to energy or electron transfer to a photoinitiator.

In those embodiments where a photosensitizer is used, the amount ofphotosensitizer utilized can vary. (As discussed above, thephotosensitizer is not necessarily present in every embodiment disclosedherein.) In certain embodiments of the first-fifth embodiments disclosedherein, when the photosensitizer is present, the actinic radiationcurable polymeric mixture comprises about 0.1 to about 5 parts by weightof the photosensitizer, including about 0.1 to about 2 parts by weight(all amounts based upon 100 total parts of polyfunctionalized dienemonomer-containing polymer and chain extender).

When a photosensitizer is utilized, various photosensitizers aresuitable for use in the actinic radiation curable polymeric mixtures. Incertain embodiments of the first-fifth embodiments disclosed herein, thephotosensitizer comprises at least one of a ketocoumarin, a xanthone, athioxanthone, a polycyclic aromatic hydrocarbon, and an oximesterderived from aromatic ketone. Exemplary ketocoumarins are disclosed inTetrahedron 38, 1203 (1982), and U.K. Patent Publication 2,083,832(Specht et al.).

Crosslinker

As discussed above, the actinic radiation curable mixture comprises apolyfunctional crosslinker reactive with the functional group F of thepolyfunctionalized diene monomer-containing polymer. Generally, thepolyfunctional crosslinker functions to increase the amount ofcrosslinking within each diene polymer chain of the polyfunctionalizeddiene monomer-containing polymer, between (separate) diene polymerchains of polyfunctionalized diene monomer-containing polymers, or both,thereby forming a network. Generally, an increased amount of crosslinkeror crosslinking will lower the Mc of the crosslinked (cured)polyfunctionalized diene monomer-containing polymer, thereby resultingin a higher modulus and a lower Eb. In certain embodiments, thepolyfunctional crosslinker is a hydrocarbon or hydrocarbon derivativepolyfunctionalized with a functional group F. In other words, such acrosslinker comprises multiple F groups. In certain embodiments, thecrosslinker is a hydrocarbon or hydrocarbon derivativepolyfunctionalized with a functional group F or a functional group thatis reactive with F. By reactive is meant a moiety that will bond with atleast two F groups of the polyfunctionalized diene monomer-containingpolymer.

Generally, the crosslinker is a polyfunctionalized hydrocarbon orhydrocarbon derivative containing at least two functional groupsreactive with F. In certain embodiments, the crosslinker isdi-functional and in other embodiments, the crosslinker istri-functional, tetra-functional, or further functionalized. While thecrosslinker is based upon a hydrocarbon or hydrocarbon derivative, itshould be understood that it can also be polymer-like in that it cancomprise either a single base unit or multiple, repeating base units.

Various compounds are suitable for use as the crosslinker. In certainembodiments, the crosslinker contains at least two (meth)acrylatefunctional groups. In certain embodiments, the crosslinker comprises apolyol (meth)acrylate prepared from an aliphatic diol, triol, or tetraolcontaining 2-100 carbon atoms; in such embodiments, the functional groupof the crosslinker is (meth)acrylate. Various crosslinkers comprising atleast two (meth)acrylate groups are commercially available. In certainembodiments, the crosslinker comprises at least one of the following:Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetraacrylate,Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate,Acrylated epoxidized soybean oil, Ditrimethylol Propane Tetraacrylate,Di-pentaerythritol Polyacrylate, Di-pentaerythritol Polymethacrylate,Di-pentaerythritol triacrylate, Di-pentaerythritol trimethacrylate,Di-pentaerythritol tetracrylate, Di-pentaerythritol tetramethacrylate,Di-pentaerythritol pent(meth)acrylate, Di-pentaerythritolhexa(meth)acrylate, Pentaerythritol Poly(meth)acrylate, Pentaerythritoltri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritolpenta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylatedglycerine triacrylate, ϵ-Caprolactone ethoxylated isocyanuric acidtriacrylate and Ethoxylated isocyanuric acid triacrylate,Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate,ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycoldi(meth)acrylate, ethyleneglycol dimethacrylate (EDMA),polyethyleneglycol di(meth)acrylates, polypropyleneglycoldi(meth)acrylates, polybutyleneglycoldi(meth)acrylates,2,2-bis(4-(meth)acryloxyethoxyphenyl) propane,2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane)tetra(meth)acrylate, and combinations thereof.

In certain embodiments, the crosslinker comprises a polyallylic compoundprepared from an aliphatic diol, triol or tetraol containing 2-100carbon atoms. Exemplary polyallylic compounds useful as crosslinkerinclude those compounds comprising two or more allylic groups,non-limiting examples of which include triallylisocyanurate (TAIC),triallylcyanurate (TAC), and the like, and combinations thereof.

In certain embodiments, the crosslinker comprises epoxy functionalgroups, aziridine functional groups, vinyl functional groups, allylfunctional groups, or combinations thereof.

In certain embodiments, the crosslinker comprises a polyfunctional aminewith at least two amine groups per molecule. In certain suchembodiments, the polyfunctional amine is an aliphatic amine. Exemplarypolyfunctional amines include, but are not limited to, diethylenetriamine, ethylene diamine, triethylene tetramine, tetraethylenepentamine, hexamethylerie diamine, 1,2-diaminocyclohexane, amino ethylpiperazine, and the like, and combinations thereof.

In certain embodiments, the polyfunctional crosslinker comprises acombination of two types of functional groups, i.e., a functional groupcapable of crosslinking at least two diene polymer chains based uponcationic radiation and a functional group capable of crosslinking atleast two diene polymer chains based upon free radical radiation. Thecombination of two types of functional groups may be present on the samepolyfunctional crosslinker or on separate crosslinkers (i.e., each withone type of functional group). In certain embodiments, thepolyfunctional crosslinker comprises a combination of at least onefunctional group selected from acrylate groups, methacrylate groups,polyallylic groups, and polyfunctional amines with at least onefunctional group selected from epoxy groups, aziridine groups, vinylgroups, and allyl groups.

Filler(s)

In certain embodiments of the first-third embodiments, the actinicradiation curable polymeric mixture further comprises at least onefiller; in certain such embodiments, the at least one filler comprises areinforcing filler, preferably a non-carbon black reinforcing filler(i.e., a reinforcing filler other than carbon black). In certainembodiments of the first-third embodiments, when at least one filler isutilized it comprises a non-carbon black filler (i.e., no carbon blackfiller is included in the at least one filler). As used herein, the term“reinforcing filler” is used to refer to a particulate material that hasa nitrogen absorption specific surface area (N₂SA) of more than about100 m²/g, and in certain instances more than 100 m²/g, more than about125 m²/g, more than 125 m²/g, or even more than about 150 m²/g or morethan 150 m²/g. Alternatively or additionally, the term “reinforcingfiller” can also be used to refer to a particulate material that has aparticle size of about 10 nm to about 50 nm (including 10 nm to 50 nm).In certain embodiments, the actinic radiation curable polymeric mixturefurther comprises at least one metal or metal oxide filler. In otherwords, the mixture further comprises at least one metal filler, at leastone metal oxide filler, or combinations thereof. Various metal fillersand metal oxide fillers are suitable for use in various embodiments ofthe actinic radiation curable polymeric mixture. In certain embodiments,the at least one metal or metal oxide filler comprises at least one of:silica (in its various forms only some of which are listed below),aluminum hydroxide, starch, talc, clay, alumina (Al₂O₃), aluminumhydrate (Al₂O₃H₂O), aluminum hydroxide (Al(OH)₃), aluminum carbonate(Al₂(CO₃)₂), aluminum nitride, aluminum magnesium oxide (MgOAl₂O₃),aluminum silicate (Al₂SiO₅, Al₄.3SiO₄.5H₂O etc.), aluminum calciumsilicate (Al₂O₃.CaO₂SiO₂, etc.), pyrofilite (Al₂O₃4SiO₂.H₂O), bentonite(Al₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin, glass balloon, glassbeads, calcium oxide (CaO), calcium hydroxide (Ca(OH)₂), calciumcarbonate (CaCO₃), magnesium carbonate, magnesium hydroxide (MH(OH)₂),magnesium oxide (MgO), magnesium carbonate (MgCO₃), magnesium silicate(Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate (CaMgSiO₄), titaniumoxide, titanium dioxide, potassium titanate, barium sulfate, zirconiumoxide (ZrO₂), zirconium hydroxide [Zr(OH)₂.nH₂O], zirconium carbonate[Zr(CO₃)₂], crystalline aluminosilicates, zinc oxide (i.e., reinforcingor non-reinforcing), and combinations thereof. graphite, clay, titaniumdioxide, magnesium dioxide, aluminum oxide (Al₂O₃), silicon nitride,calcium silicate (Ca₂SiO₄, etc.), crystalline aluminosilicates, siliconcarbide, single walled carbon nanotubes, double walled carbon nanotubes,multi walled carbon nanotubes, grapheme oxide, graphene, silver, gold,platinum, copper, strontium titanate (StTiO₃), barium titanate (BaTiO₃),silicon (Si), hafnium dioxide (HfO₂), manganese dioxide (MnO₂), ironoxide (Fe₂O₄ or Fe₃O₄), cerium dioxide (CeO₂), copper oxide (CuO),indium oxide (In₂O₃), indium tin oxide (In₂O₃ SnO₂). In certainembodiments, the at least one filler comprises at least one of: silica(in its various forms only some of which are listed below), aluminumhydroxide, starch, talc, clay, alumina (Al₂O₃), aluminum hydrate(Al₂O₃H₂O), aluminum hydroxide (Al(OH)₃), aluminum carbonate(Al₂(CO₃)₂), aluminum nitride, aluminum magnesium oxide (MgOAl₂O₃),aluminum silicate (Al₂SiO₅, Al₄.3SiO₄.5H₂O etc.), aluminum calciumsilicate (Al₂O₃.CaO₂SiO₂, etc.), pyrofilite (Al₂O₃4SiO₂.H₂O), bentonite(Al₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin, glass balloon, glassbeads, calcium oxide (CaO), calcium hydroxide (Ca(OH)₂), calciumcarbonate (CaCO₃), magnesium carbonate, magnesium hydroxide (MH(OH)₂),magnesium oxide (MgO), magnesium carbonate (MgCO₃), magnesium silicate(Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate (CaMgSiO₄), titaniumoxide, titanium dioxide, potassium titanate, barium sulfate, zirconiumoxide (ZrO₂), zirconium hydroxide [Zr(OH)₂.nH₂O], zirconium carbonate[Zr(CO₃)₂], crystalline aluminosilicates, zinc oxide (i.e., reinforcingor non-reinforcing), and combinations thereof graphite, clay, titaniumdioxide, magnesium dioxide, aluminum oxide (Al₂O₃), silicon nitride,calcium silicate (Ca₂SiO₄, etc.), crystalline aluminosilicates, siliconcarbide, single walled carbon nanotubes, double walled carbon nanotubes,multi walled carbon nanotubes, grapheme oxide, graphene, silver, gold,platinum, copper, strontium titanate (StTiO₃), barium titanate (BaTiO₃),silicon (Si), hafnium dioxide (HfO₂), manganese dioxide (MnO₂), ironoxide (Fe₂O₄ or Fe₃O₄), cerium dioxide (CeO₂), copper oxide (CuO),indium oxide (In₂O₃), indium tin oxide (In₂O₃ SnO₂).

In certain embodiments of the first-third embodiments, the at least onefiller includes ground, cured rubber, optionally in combination with oneof more of the foregoing fillers. As used herein, the term “ground,cured rubber” refers to cured, i.e., vulcanized (crosslinked) rubberthat has been ground or pulverized into particulate matter; variousparticle size ground, cured rubber may be utilized. In certainembodiments of the first-third embodiments where ground, cured rubber isutilized, it has an average particle size in the range of about 50 μm toabout 250 μm (including 50 μm to 250 μm), preferably an average particlesize of about 74 μm to about 105 μm (including 74 μm to 105 μm. Theaverage particle size of ground, cured rubber particles may be measuredby any conventional means known in the art including the methodsaccording to ASTM D5644. Examples of suitable sources of rubber for theground, cured rubber include used tires. It is well known to thoseskilled in the art that tires are prepared from natural and syntheticrubbers that are generally compounded using fillers including carbonblack and sometimes also including silica. The source of the ground,cured rubber used in accordance with the first, second, and thirdembodiments disclosed herein may vary, but in certain embodiments can betires (or rubber from such tires) produced with a carbon black filler,with a silica filler, or with mixtures of both. Exemplary sourcesinclude tires from passenger cars, light trucks, or combinations ofboth. In certain embodiments of the first-third embodiments whereground, cured rubber is utilized, the ground, cured rubber is free ofcarbon black filler (i.e., the ground, cured rubber contains less than 1phr carbon black filler or even 0 phr carbon black filler).

When at least one filler is utilized in the actinic radiation curablepolymeric mixture, the total amount utilized may vary widely. Generally,the total amount of filler utilized will vary depending upon the type offiller and the properties sought in the cured polymeric mixture producedfrom the atcinic radiation curable polymeric mixture. As well, incertain embodiments, the amount of filler will also be adjusted basedupon any viscosity increase that it causes to the overall atcinicradiation curable polymeric mixture. In certain embodiments, the totalamount of filler utilized in the actinic radiation curable polymericmixture is an amount that does not cause the viscosity of the mixture toexceed about 10,000 cps (at 25° C.), preferably not exceeding about5,000 cps (at 25° C.). In certain embodiments of the first-fifthembodiments disclosed herein, the at least one filler is present in atotal amount (i.e, the total of amount of all fillers if more than oneis present) of up to about ⅔ (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%,35%, 30%, 25%, 20%, 15%, 10%, 5%, 2%, or 1%) of the total volume of theactinic radiation curable polymeric mixture. In certain embodiments ofthe first-fifth embodiments disclosed herein, the at least one filler ispresent in a total amount (i.e, the total of amount of all fillers ifmore than one is present)of about 40 to about 80 parts (based upon 100total parts of (a) and (b)), including 40 parts, 45 parts, 50 parts, 55parts, 60 parts, 65 parts, 70 parts, 75 parts and 80 parts. In certainembodiments of the first-third embodiments disclosed herein, the onlyfillers utilized are non-carbon black fillers and the total amount ofall non-carbon black fillers (i.e, the total of amount of all non-carbonblack fillers if more than one is present) is of up to about ⅔ of thetotal volume (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%,20%, 15%, 10%, 5%, 2%, or 1%) of the actinic radiation curable polymericmixture. In certain embodiments of the first-third embodiments disclosedherein, the only fillers utilized are non-carbon black fillers and thetotal amount of all non-carbon black fillers (i.e, the total of amountof all non-carbon black fillers if more than one is present) is about 40to about 80 parts (based upon 100 total parts of (a) and (b)).

In certain embodiments of the first-third embodiments, at least onecarbon black filler is utilized; in such embodiments the at least onecarbon black filler may be utilized as the only filler but mayalternatively be utilized in combination with one or more non-carbonblack filler such as those discussed above. In those embodiments of thefirst-third embodiments disclosed herein that include at least onecarbon black filler, the total amount of carbon black filler can varyand may include amounts such as at least 0.01 parts, 0.01 to less than 1part, 0.05 to 0.5 parts (based upon 100 total parts of (a) and (b)).

In those embodiments of the first-third embodiments where at least onecarbon black is utilized as a filler, various carbon blacks can beutilized. In certain embodiments of the first-third embodiments, one ormore reinforcing carbon blacks are utilized. In other embodiments of thefirst-third embodiments, one or more non-reinforcing carbon blacks areutilized. In yet other embodiments of the first-third embodiments, atleast one reinforcing carbon black is used in combination with at leastone non-reinforcing carbon black. Carbon blacks having a nitrogensurface area of greater than 30 m²/g and a DBP absorption of greaterthan 60 cm³/100 g) are referred to herein as “reinforcing carbon blacks”and carbon blacks having a lower nitrogen surface area and/or lower DBPabsorption are referred to herein as “non-reinforcing carbon blacks.”The nitrogen surface area and the DBP absorption provide respectivecharacterizations of the particle size and structure of the carbonblack. The nitrogen surface area is a conventional way of measuring thesurface area of carbon black. Specifically, the nitrogen surface area isa measurement of the amount of nitrogen which can be absorbed into agiven mass of carbon black. Preferably, the nitrogen surface area forcarbon black fillers is determined according to ASTM test D6556 orD3037. The DBP absorption is a measure of the relative structure ofcarbon black determined by the amount of DBP a given mass of carbonblack can absorb before reaching a specified viscous paste. Preferably,the DBP absorption for carbon black fillers is determined according toASTM test D2414. Among the useful carbon blacks are furnace black,channel blacks, and lamp blacks. More specifically, examples of usefulcarbon blacks include super abrasion furnace (SAF) blacks, high abrasionfurnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace(FF) blacks, intermediate super abrasion furnace (ISAF) blacks,semi-reinforcing furnace (SRF) blacks, medium processing channel blacks,hard processing channel blacks and conducting channel blacks. Exemplaryreinforcing carbon blacks include: N-110, N-220, N-339, N-330, N-351,N-550, and N-660, and combinations thereof. Exemplary non-reinforcingcarbon blacks include: thermal blacks or the N9 series carbon blacks(also referred to as the N-900 series), such as those with the ASTMdesignation N-907, N-908, N-990, and N-991.

Container(s) (e.g., Cartridge(s))

In certain embodiments, the actinic radiation curable polymeric mixtureis packaged into a cartridge or other container suitable for shipping orstorage. As discussed above, a cartridge is a container adapted for orconfigured for use in an additive manufacturing device; other types ofcontainers may be useful such as for shipping or storage, and the termcontainer should be considered as inclusive of, but not limited to, acartridge.

Various combinations of one or more containers (or cartridges) tocontain the ingredients of the actinic radiation curable polymericmixture in its various sub-embodiments (as described above) areenvisioned. In certain embodiments, at least two containers (orcartridges) are utilized, with one container (or cartridge) comprising:the polyfunctionalized diene monomer-containing polymer having theformula [P][F]_(n) where P represents a diene polymer chain, Frepresents a functional group, n is 2 to about 15, and each F can be thesame or different and chain extender based upon F or reactive with F andthe second container (or cartridge) comprising chain extender based uponF or reactive with F along with at least one of an actinic radiationsensitive photoinitiator and a photosensitizer. In certain of theforegoing embodiments, the second container (or cartridge) furthercomprises a crosslinker reactive with F; alternatively, a thirdcontainer (or cartridge) comprising a crosslinker reactive with F can beprovided. In certain embodiments, a kit is provided for producing anelastomeric cured product by additive printing comprising at least twocontainers (or cartridges) as previously described. In certainembodiments, the kit comprises at least two containers (or cartridges),wherein at least one container (or cartridge) comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and a chain extender based upon F or compatible with F; and atleast a second container (or cartridge) comprises a chain extender basedupon F or compatible with F, at least one of an actinic radiationsensitive photoinitiator and a photosensitizer, and optionally acrosslinker reactive with F. In certain of the foregoing embodiments ofthe kit and containers (or cartridges), wherein at least one of thefirst or second container (or cartridge) further comprises at least onemetal or metal oxide filler. In certain of the foregoing embodiments ofthe kit and containers (or cartridges), wherein at least one of thefirst or second container (or cartridge) further comprises at least onefiller (as discussed below).

Cured Elastomeric/Polymeric Product/Article

As discussed above, the second embodiment disclosed herein is directedto a cured polymeric mixture. In certain embodiments of the secondembodiment, the cured polymeric mixture comprises a crosslinkedpolyfunctionalized diene polymer comprising a diene polymer chainbackbone [P], multiple functional groups F where each F is the same ordifferent, and crosslinkages between pairs of functional groups. Inother embodiments of the second embodiment, the cured polymeric mixturecan be understood as comprising a cured version of the actinic radiationcurable polymeric mixture as previously described (i.e., according tothe first embodiment described herein). It should be understood thatdescriptions of the ingredients of the actinic radiation curablepolymeric mixture are intended to apply to the fullest extent possibleto certain embodiments of the cured polymeric mixture, as if fully setforth with specific language directed to the cured polymeric mixture ofthe second embodiment.

In certain embodiments of the second embodiment, the cured polymericmixture comprises an elastomeric polymeric mixture. In certainembodiments of the second embodiment, the cured polymeric mixture iselastomeric. As used herein, the term elastomeric can be understoodaccording to the following explanation. Yield as used herein refers tothe onset of plastic deformation in a material under an applied load.Plastic deformation is deformation that remains after the load isremoved. The yield point is the peak in a load-elongation curve (load ony axis, elongation on x axis) at which plastic flow becomes dominant.Thus, as used herein, the term elastomer or elastomeric refers to amaterial which does not exhibit any definite yield point or area ofplastic deformation; in other words, the deformation of an elastomericmaterial remains elastic as opposed to becoming plastic.

In certain embodiments of the second embodiment, the cured elastomericmixture comprises crosslinkages which contain no sulfur. In certainembodiments of the second embodiment, the cured elastomeric mixturecomprises crosslinkages which are essentially free of sulfur. Byessentially free of sulfur is meant that no more than about 1 ppm ofsulfur in the overall actinic radiation curable polymeric mixture of thecured polymeric mixture, including less than 1 ppm, less than about 0.1ppm, less than 0.1 ppm, and 0 ppm. In certain embodiments of the secondembodiment, the cured elastomer mixture comprises crosslinkages whichcontain sulfur, various amounts of which are possible.

Processes for Producing a Cured Elastomeric Product/Article

As discussed above, the third embodiment disclosed herein is directed toa process for producing a cured polymeric product. This processcomprises providing an additive manufacturing device comprising a sourceof actinic radiation, an exterior support structure, an interior tankcapable of containing a liquid mixture, and an interior supportstructure; providing a liquid mixture comprising an actinic radiationcurable polymeric mixture according to the first embodiments disclosedherein (i.e., as previously described) to the interior tank; repeatedlyforming upon a support structure a layer from the liquid mixture; usingactinic radiation to cure each layer; thereby producing a curedpolymeric product. According to the third embodiment disclosed herein,various types of additive manufacturing devices may be utilized.Generally, a great variety of additive manufactures devices arecommercially available from companies including, but not limited to, 3DSystems, Inc. (Rock Hill, S.C.) and Stratasys Ltd. (Eden Prairie,Minn.). In certain embodiments, the additive manufacturing device formsthe product by a process that comprises solidifying each layer by usingthe actinic radiation to trace a pattern in the liquid material; incertain such embodiments the device contains no printer head; in certainsuch embodiments, such a process can be referred to as vatphotopolymerization. In certain embodiments of the third embodiment, theadditive manufacturing device forms the product by a process thatcomprises solidifying each layer by using actinic radiation to provideat least one pattern on the liquid material, such a process can bereferred to as laser rastering. In certain embodiments of the thirdembodiment, the laser rastering can be understood as involving the useof pinpoint radiation which is moved across the service to result in anoverall pattern being provided. In certain embodiments of the thirdembodiment, the additive manufacturing device forms the product by aprocess that comprises solidifying each layer by using actinic radiationto project at least one image on the liquid material, such a process canbe referred to as digital light processing. As used herein, the phrasetracing a pattern in the liquid material is intended to encompass bothdigital light processing and laser rastering processes. In otherembodiments, the additive manufacturing device forms the product bydispensing the mixture from a printing head having a set of nozzles; incertain such embodiments, such a process can be referred to as materialjetting.

According to the process of the third embodiment, the thickness of eachlayer that is formed by the additive manufacturing device (e.g., uponthe support structure) may vary. In certain embodiments, each layer hasa thickness of about 0.01 mm to about 1 mm, including a thickness of0.01 mm to 1 mm, about 0.1 mm to about 0.3 mm, and 0.1 mm to 0.3 mm.According to the third embodiment, the materials of construction for thesupport structure of the additive manufacturing device upon which theproduct is formed may vary. In certain embodiments of the thirdembodiment, the support structure comprises polysiloxane polymer (e.g.,polydimethylsiloxane or PDMS), a halogenated polymer coating, ahalogenated wax coating, or a combination thereof. Non-limiting examplesof halogenated polymer coatings include fluorinated halogenated polymerssuch as polytetrafluoroethylene (PTFE, sold under the tradename Teflon®by DuPont). Non-limiting examples of halogenated wax coatings includefluorinated waxes, chlorinated waxes, brominated waxes, and combinationsthereof. Various commercial sources for halogenated waxes exist such asDover Chemical Corporation (Dover, Ohio) which sells Doverguard® brandbrominated waxes and Chlorez® brand chlorinated waxes. Use of theforegoing materials of construction for the support structure oremploying those materials as a coating for the support structure uponwhich the product is formed can facilitate the processes of the thirdembodiment and production of the resulting products by enabling theproduct to be more easily removed from the support structure, preferablywithout curing or otherwise sticking to the support structure such thatremoval therefrom involves tearing or breaking one or more layers of theproduct. As those of skill in the art will appreciate, the particularmaterial of construction used for the support structure may beintentionally varied depending upon the ingredients contained in theactinic radiation curable polymeric mixture (in particular, the type ofchain extender utilized).

The wavelength of the actinic radiation used in the processes of thethird embodiment disclosed herein may vary, depending upon theparticular type of additive manufacturing device chosen or the settingchosen for a particular additive manufacturing devices (some devicesallow the user to select different wavelength ranges). In certainembodiments, the actinic radiation has a wavelength in the UV to Visiblerange. In certain embodiments, the actinic radiation (light) has awavelength of about 320 to less than 500 nm, including about 350 toabout 450 nm, and about 365 to about 405 nm.

In certain embodiments of the processes of the third embodimentdisclosed herein, the process includes the use of a cartridge to providethe liquid mixture comprising the actinic radiation curable polymericmixture. In certain embodiments of the processes of the third embodimentdisclosed herein, the interior tank of the additive manufacturing devicefurther comprises a component capable of receiving a liquid mixture fromat least one cartridge. In other words, in such embodiments, theinterior tank of the additive manufacturing device is capable ofreceiving a liquid mixture from at least one cartridge.

Various combinations of one or more cartridges to contain theingredients of the actinic radiation curable polymeric mixture in itsvarious sub-embodiments (as described above) are envisioned for use incertain embodiments of the processes of the third embodiment. In certainembodiments of the third embodiment, the process comprises the use of atleast two cartridges, with one cartridge comprising: thepolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and chain extender based upon F or reactive with F and thesecond cartridge comprising chain extender based upon F or reactive withF along with at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer. In certain of the foregoingembodiments, the second cartridge further comprises a crosslinkerreactive with F; alternatively, a third cartridge comprising acrosslinker reactive with F can be provided.

Kits

According to a fourth embodiment, a kit is provided comprising at leasttwo containers or cartridges as previously described is provided. Suchkits can be useful in producing an cured polymeric product by additiveprinting. For example, by the use of such kits, a manufacturer mayutilize different types and combinations of polyfunctionalized dienemonomer-containing polymer(s), chain extender(s), photoinitiator(s),photosensitizer(s), and crosslinker(s). The use of a kit with multiplecartridges or containers could provide an advantage in material jettingprocesses where the machine and print head could be used to selectivelydispense the materials from different cartridges or containers withoutthe need to pre-mix the materials. Use of a kit comprising at least onecartridge or container with at least one filler would allow for thefiller to be in a stable dispersion and mixed (as needed) with the othercomponents either just prior to or upon printing. In certainembodiments, the kit comprises at least two containers or cartridges,wherein at least one container (or cartridge) comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and a chain extender based upon F or compatible with F; and atleast a second container (or cartridge) comprises a chain extender basedupon F or compatible with F, at least one of an actinic radiationsensitive photoinitiator and a photosensitizer, and optionally acrosslinker reactive with F. In certain of the foregoing embodiments ofthe kit, at least one container or cartridge further comprises at leastone metal or metal oxide filler. In certain of the foregoing embodimentsof the kit, at least one container or cartridge further comprises atleast one filler (as discussed above). The particular ingredients ofeach container or cartridge used in a kit can vary in conjunction withthe description of the actinic radiation curable polymeric mixture aspreviously described.

Tires and Tire Components

As discussed above, the fifth embodiment disclosed herein is directed toa tire comprising at least one component comprised of the curedpolymeric mixture according to second embodiment disclosed herein (asdescribed above) or the actinic radiation curable polymeric mixture ofthe first embodiment (as described above) that has been cured. Asmentioned above, descriptions of the ingredients of the actinicradiation curable polymeric mixture apply to the fullest extent possibleto certain embodiments of the cured polymeric mixture, as if fully setforth with specific language directed to the cured polymeric mixture ofthe second embodiment. Likewise, it should be understood thatdescriptions of the cured polymeric mixture and the actinic radiationcurable polymeric mixture apply to the fullest extent possible tocertain embodiments of the tires and tire components, as if fully setforth with specific language directed to the tires and tire componentsof the fifth embodiment.

In certain embodiments of the fifth embodiment, the component of thetire comprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured comprisesat least one of: a tread, a bead, a sidewall, an innerliner, and asubtread. In certain embodiments of the fifth embodiment, the componentof the tire comprising at least one component comprised of the curedpolymeric mixture according to second embodiment disclosed herein (asdescribed above) or the actinic radiation curable polymeric mixtureaccording to the first embodiment (as described above) that has beencured comprises a tire tread. In other words, disclosed herein is a tiretread comprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured. Incertain embodiments of the fifth embodiment, the component of the tirecomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) r the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured comprisesa subtread. In other words, disclosed herein is a tire subtreadcomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured. Incertain embodiments of the fifth embodiment, the component of the tirecomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured comprisesa tire sidewall. In other words, disclosed herein is a tire sidewallcomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured. Incertain embodiments of the fifth embodiment, the component of the tirecomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured comprisesa tire bead. In other words, disclosed herein is a tire bead comprisingat least one component comprised of the cured polymeric mixtureaccording to second embodiment disclosed herein (as described above) orthe actinic radiation curable polymeric mixture according to the firstembodiment (as described above) that has been cured. In certainembodiments of the fifth embodiment, the component of the tirecomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured comprisesa tire innerliner. In other words, disclosed herein is a tire innerlinercomprising at least one component comprised of the cured polymericmixture according to second embodiment disclosed herein (as describedabove) or the actinic radiation curable polymeric mixture according tothe first embodiment (as described above) that has been cured.

Manufacturing a tire component (e.g., treads, beads, sidewalls,innerliners or subtreads) by an additive manufacturing process using theactinic radiation curable polymeric mixtures disclosed herein oraccording to the processes of the third embodiment disclosed herein canprovide an advantage in terms of being able to produce shapes and designthat cannot be produced using traditional manufacturing processes suchas molding. As a non-limiting example, in certain embodiments of thefifth embodiment, wherein the at least one component of the tirecomprises a tread, a tread can be produced that includes at least one ofthe following: a closed hollow void, an undercut void, and an overhungvoid. As used herein, the phrase “closed hollow void” refers to a voidthat is not open to the road-contacting surface of the tread (at leastnot upon manufacture); the particular shape of the closed hollow is notparticularly limited and shapes that are circular, elliptical, square,rectangular, trapezoidal, rectangular, and triangular may be utilized invarious embodiments. Non-limiting examples of closed hollow voids areprovided in FIG. 1. As used herein, the phrase “overhung void” refers toa void that is partially open to the road-contacting surface of thetread (upon manufacture), that is wider (in at least one dimension) thanthe opening, and that includes upper walls (at the road-contactingsurface) having a thickness less than the overall depth of the void andprojecting over and partially covering the opening to theroad-contacting surface of the tread. Non-limiting examples of overhungvoids are provided in FIG. 2. As used herein, the phrase “undercut void”refers to a void that is partially open to the road-contacting surfaceof the tread (upon manufacture), that is wider (in at least onedimension) than the opening, and that includes upper walls (at theroad-contacting surface) that partially extend into the void withouthanging over the void. In certain embodiments, the undercut void hasunsupported walls angled (from the bottom towards the top) generallytoward the opening to the road-contacting surface. In certainembodiments, the overhung void has unsupported walls that aresubstantially parallel (+ or − about 5°) to the road-contacting surfaceor have angles (from the bottom towards the top) generally directed awayfrom the opening to the road-contacting surface. Non-limiting examplesof overhung voids are provided in FIG. 3.

Other Rubber Goods

In certain embodiments, a rubber good other than a tire or tirecomponent is made from (i.e., comprises) the cured polymeric mixtureaccording to second embodiment disclosed herein (as described above) orthe actinic radiation curable polymeric mixture of the first embodiment(as described above) that has been cured. As mentioned above,descriptions of the ingredients of the actinic radiation curablepolymeric mixture apply to the fullest extent possible to certainembodiments of the cured polymeric mixture, as if fully set forth withspecific language directed to the cured polymeric mixture of the secondembodiment. Likewise, it should be understood that descriptions of thecured polymeric mixture and the actinic radiation curable polymericmixture apply to the fullest extent possible to certain rubber goodsembodiments, as if fully set forth with specific language directed tosuch rubber goods of the sixth embodiment.

In certain embodiments of the sixth embodiment, the rubber goodcomprising the cured polymeric mixture according to second embodimentdisclosed herein (as described above) or the actinic radiation curablepolymeric mixture according to the first embodiment (as described above)that has been cured comprises at least one of: a bushing, a seal, agasket, a conveyor belt, a hose, or a glove (or gloves). In certainembodiments of the sixth embodiment, the rubber good comprising thecured polymeric mixture according to second embodiment disclosed herein(as described above) or the actinic radiation curable polymeric mixtureaccording to the first embodiment (as described above) that has beencured comprises a bushing. In other words, disclosed herein is a bushingcomprising the cured polymeric mixture according to second embodimentdisclosed herein (as described above) or the actinic radiation curablepolymeric mixture according to the first embodiment (as described above)that has been cured. In certain embodiments of the sixth embodiment, therubber good comprising the cured polymeric mixture according to secondembodiment disclosed herein (as described above) or the actinicradiation curable polymeric mixture according to the first embodiment(as described above) that has been cured comprises a seal. In otherwords, disclosed herein is a seal comprising the cured polymeric mixtureaccording to second embodiment disclosed herein (as described above) orthe actinic radiation curable polymeric mixture according to the firstembodiment (as described above) that has been cured. In certainembodiments of the sixth embodiment, the rubber good comprising thecured polymeric mixture according to second embodiment disclosed herein(as described above) or the actinic radiation curable polymeric mixtureaccording to the first embodiment (as described above) that has beencured comprises a gasket. In other words, disclosed herein is a gasketcomprising the cured polymeric mixture according to second embodimentdisclosed herein (as described above) or the actinic radiation curablepolymeric mixture according to the first embodiment (as described above)that has been cured. In certain embodiments of the sixth embodiment, therubber good comprising the cured polymeric mixture according to secondembodiment disclosed herein (as described above) or the actinicradiation curable polymeric mixture according to the first embodiment(as described above) that has been cured comprises a conveyor belt. Inother words, disclosed herein is a conveyor belt comprising the curedpolymeric mixture according to second embodiment disclosed herein (asdescribed above) or the actinic radiation curable polymeric mixtureaccording to the first embodiment (as described above) that has beencured. In certain embodiments of the sixth embodiment, the rubber goodcomprising the cured polymeric mixture according to second embodimentdisclosed herein (as described above) or the actinic radiation curablepolymeric mixture according to the first embodiment (as described above)that has been cured comprises a hose. In other words, disclosed hereinis a hose comprising the cured polymeric mixture according to secondembodiment disclosed herein (as described above) or the actinicradiation curable polymeric mixture according to the first embodiment(as described above) that has been cured. In certain embodiments of thesixth embodiment, the rubber good comprising the cured polymeric mixtureaccording to second embodiment disclosed herein (as described above) orthe actinic radiation curable polymeric mixture according to the firstembodiment (as described above) that has been cured comprises a glove orgloves. In other words, disclosed herein is a glove or gloves comprisingthe cured polymeric mixture according to second embodiment disclosedherein (as described above) or the actinic radiation curable polymericmixture according to the first embodiment (as described above) that hasbeen cured.

Manufacturing rubber goods (e.g., bushings, seals, gaskets, conveyorbelts, hoses, or gloves) by an additive manufacturing process using theactinic radiation curable polymeric mixtures disclosed herein oraccording to the processes of the third embodiment disclosed herein canprovide an advantage in terms of being able to produce shapes anddesigns that cannot be produced using traditional manufacturingprocesses such as molding. As a non-limiting example a hose manufacturedby an additive manufacturing process using the actinic radiation curablepolymeric mixtures disclosed herein or according to the processes of thethird embodiment disclosed herein could include internal structure(s)such as multiple channels (to allow separate passage of ingredientsthrough a portion of the hose) or internal projections, protrusions orother internal structure(s) to effect mixing of ingredients during flowthrough the hose. Another non-limiting example includes the ability tomanufacture custom-fitting or custom sized gloves without the need forproduction of a custom form or a multitude of forms in different sizes.

Exemplary Embodiments of the First-Sixth Embodiments

The following exemplary embodiments or sub-embodiments of thefirst-fifth embodiments should be considered to be specificallydisclosed herein. Item 1. An actinic radiation curable polymeric mixturecomprising: (a) a polyfunctionalized diene monomer-containing polymerhaving the formula: [P][F]_(n) where P represents a diene polymer chain,F represents a functional group, n is 2 to about 15, and each F can bethe same or different; (b) optionally a chain extender based upon F orreactive with F; (c) at least one actinic radiation sensitivephotoinitiator; (d) optionally, a photosensitizer; and (e) apolyfunctional crosslinker reactive with F. Item 2. The actinicradiation curable polymeric mixture of item 1, wherein the total amountof (a) and (b) is 100 parts and (c) is present in a total amount of atleast about 0.1 parts (based upon 100 parts of (a) and (b)). Item 3. Theactinic radiation curable polymeric mixture of item 1 or item 2, whereinthe mixture is curable by UV-VIS light. Item 4. The actinic radiationcurable polymeric mixture according to any one of items 1-3, wherein (a)is present in an amount of 1-100 parts and (b) is present in an amountof 0-99 parts. Item 5. The actinic radiation curable polymeric mixtureaccording to any one of items 1-4, wherein the at least one actinicsensitive photoinitiator is present in an amount of about 1 part toabout 10 parts (per 100 total parts of (a) and (b)). Item 6. The actinicradiation curable polymeric mixture according to any one of items 1-5,wherein the photosensitizer is present in an amount of about 0.1 partsto about 5 parts (per 100 total parts of (a) and (b)). Item 7. Theactinic radiation curable polymeric mixture according to any one ofitems 1-6, wherein each F comprises at least one of: acrylate,methacrylate, cyanoacrylate, epoxide, aziridine, and thioepoxide. Item8. The actinic radiation curable polymeric mixture according to any oneof items 1-7, wherein F comprises an acrylate or methacrylate, whenpresent the chain extender comprises an acrylate-based chain extender,and when present the crosslinker comprises a poly acrylate-basedcrosslinker. Item 9. The actinic radiation curable polymeric mixtureaccording to any one of items 1-8, wherein F comprises a free radicalpolymerizable functionalizing group. Item 10. The actinic radiationcurable polymeric mixture according to any one of items 1-9, wherein Fcomprises a cationic polymerizable functionalizing group. Item 11. Theactinic radiation curable polymeric mixture according to any one ofitems 1-8, wherein F comprises a combination of cationic polymerizableand free radical polymerizable functional groups either on the samediene polymer chain or on separate diene polymer chains. 12. The actinicradiation curable polymeric mixture according to any one of items 1-11,wherein the polyfunctionalized diene monomer-containing polymer has a Mnof about 3,000 to about 135,000 grams/mole (polystyrene standard). Item13. The actinic radiation curable polymeric mixture according to any oneof items 1-12, wherein the diene polymer chain comprises monomersselected from at least one of: acyclic and cyclic dienes having 3 toabout 15 carbon atoms. Item 14. The actinic radiation curable polymericmixture according to any one of items 1-13, wherein the diene polymerchain comprises monomers selected from at least one of: 1,3-butadiene,isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene,and substituted derivatives of each of the foregoing. Item 15. Theactinic radiation curable polymeric mixture according to any one ofitems 1-14, comprising a polyfunctional crosslinker selected from polyol(meth)acrylates prepared from an aliphatic diol, triol, or tetraolcontaining 2-100 carbon atoms, polyallylic compounds prepared from analiphatic diol, triol or tetraol containing 2-100 carbon atoms,polyfunctional amines, or combinations thereof. Item 16. The actinicradiation curable polymeric mixture according to any one of items 1-15,comprising a polyfunctional crosslinker selected from at least one of:Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetraacrylate,Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate,Acrylated epoxidized soybean oil, Ditrimethylol Propane Tetraacrylate,Di-pentaerythritol Polyacrylate, Di-pentaerythritol Polymethacrylate,Di-pentaerythritol triacrylate, Di-pentaerythritol trimethacrylate,Di-pentaerythritol tetracrylate, Di-pentaerythritol tetramethacrylate,Di-pentaerythritol pent(meth)acrylate, Di-pentaerythritolhexa(meth)acrylate, Pentaerythritol Poly(meth)acrylate, Pentaerythritoltri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritolpenta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylatedglycerine triacrylate, ϵ-Caprolactone ethoxylated isocyanuric acidtriacrylate and Ethoxylated isocyanuric acid triacrylate,Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate,ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycoldi(meth)acrylate, ethyleneglycol dimethacrylate (EDMA),polyethyleneglycol di(meth)acrylates, polypropyleneglycoldi(meth)acrylates, polybutyleneglycol di(meth)acrylates,2,2-bis(4-(meth)acryloxyethoxyphenyl) propane,2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane)tetra(meth)acrylate, and combinations thereof. Item 17. The actinicradiation curable polymeric mixture according to item 13 or item 14,wherein the diene polymer chain further comprises at least one vinylaromatic monomer. Item 18. The actinic radiation curable polymericmixture according to any one of items 1-17, wherein the Tg of thepolyfunctionalized diene polymer is about −105 to about −10° C. Item 19.The actinic radiation curable polymeric mixture according to any one ofitems 1-18, wherein the chain extender comprises an (meth)acrylatemonomer selected from C2 to about C18 alkyl functionalized(meth)acrylates. Item 20. The actinic radiation curable polymericmixture according to any one of items 1-29, wherein the Tg of the chainextender is about −65 to about 10° C. Item 21. The actinic radiationcurable polymeric mixture according to any one of item 1-20, wherein thechain extender has a Mw of about 72.06 to about 135,000 grams/mole. Item22. The actinic radiation curable polymeric mixture according to any oneof items 1-21, wherein the photosensitizer comprises at least one of aketocoumarin, a xanthone, a thioxanthone, a polycyclic aromatichydrocarbon, and an oximester derived from aromatic ketone. Item 23. Theactinic radiation curable polymeric mixture according to any one ofitems 1-22, wherein the photoinitiator comprises at least one of: abenzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromaticα-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, abis-acylphosphinoxide, and a tris-acylphosphinoxide Item 24. The actinicradiation curable polymeric mixture according to any one of items 1-23,wherein the photoinitiator is selected from benzophenone,benzildimethylketal, 1-hydroxy-cyclohexyl-phenyl-ketone,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-lone,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one,(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,(4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane,(2,4,6-trimethylbenzoyl)diphenylphosphine oxide,bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propan-1-one,1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime),oligo[2-hydroxy-2-methyl-1-[4-methylvinyl]phenyl]propanone,2-hydroxy-2-methyl-1-phenyl propan-1-one, and combinations thereof. Item25. The actinic radiation curable polymeric mixture according to any oneof items 1-24, wherein the photoinitiator comprises at least one of: abenzoin, an aryl ketone, an alpha-amino ketone, a mono- orbis(acyl)phosphine oxide, a benzoin alkyl ether, a benzil ketal, aphenylglyoxalic ester or derivatives thereof, an oxime ester, aper-ester, a ketosulfone, a phenylglyoxylate, a borate, and ametallocene. Item 26. The actinic radiation curable polymeric mixtureaccording to any one of items 1-25, further comprising at least onemetal or metal oxide filler. Item 27. The actinic radiation curablepolymeric mixture according to item 26, wherein the at least one metalor metal oxide filler is present in an amount of up to about ⅔ of thetotal volume of the actinic radiation curable polymeric mixture. Item28. The actinic radiation curable polymeric mixture according to item26, wherein the at least one metal or metal oxide filler is present inan amount of about 40 to about 80 parts (based upon 100 total parts of(a) and (b)). Item 29. The actinic radiation curable polymeric mixtureaccording to any one of item 1-28, wherein the mixture has a viscosityat 25° C.) of about 1 to about 10,000 cps, preferably about 100 to about5,000 cps. Item 30. A cartridge containing the actinic radiation curablepolymeric mixture according to any one of items 1-29.

Item 100. A cured polymeric mixture comprising: a crosslinkedpolyfunctionalized diene polymer comprising a diene polymer chainbackbone [P], multiple functional groups F where each F is the same ordifferent, and crosslinkages between pairs of functional groups. Item101. The cured polymeric mixture according to item 100, wherein each Fcomprises at least one of: acrylate, methacrylate, cyanoacrylate,epoxide, aziridine, and thioepoxide. Item 102. The cured polymericmixture according to any one of items 101-101, wherein F comprises anacrylate or methacrylate, when present the chain extender comprises anacrylate-based chain extender, and when present the crosslinkercomprises a poly acrylate-based crosslinker. Item 103. The curedpolymeric mixture according to any one of items 100-102, wherein Fcomprises a free radical polymerizable functionalizing group. Item 104.The cured polymeric mixture according to any one of items 100-102,wherein F comprises a cationic polymerizable functionalizing group. Item105. The cured polymeric mixture according to any one of items 100-102,wherein F comprises a combination of cationic polymerizable and freeradical polymerizable functional groups either on the same diene polymerchain or on separate diene polymer chains. Item 106. The cured polymericmixture according to any one of items 100-105, wherein the diene polymerchain comprises monomers selected from at least one of: acyclic andcyclic dienes having 3 to about 15 carbon atoms. Item 107. The curedpolymeric mixture according to any one of items 100-106, wherein thediene polymer chain comprises monomers selected from at least one of:1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene,and substituted derivatives of each of the foregoing. Item 108. Thecured polymeric mixture according to item 106 or 107, wherein the dienepolymer chain further comprises at least one vinyl aromatic monomer.Item 109. The cured polymeric mixture according to any one of items100-108, further comprising at least one metal or metal oxide filler.Item 110. The cured polymeric mixture according to item 109, wherein theat least one metal or metal oxide filler is present in an amount of upto about ⅔ of the total volume of The cured polymeric mixture. Item 111.The cured polymeric mixture according to item 109, wherein the at leastone metal or metal oxide filler is present in an amount of about 40 toabout 80 parts (based upon 100 total parts of the crosslinkedpolyfunctionalized diene polymer. Item 112. A cured polymeric mixturecomprising the cured polymeric mixture according to any one of items1-29. Item 113. The cured polymeric mixture according to item 112,wherein the polyfunctionalized diene monomer-containing polymer iscrosslinked between F groups. Item 114. The cured polymeric mixtureaccording to any one of items 100-113, wherein the mixture comprises a3-dimensional article. Item 115. The cured polymeric mixture accordingto any one of items 100-114, wherein the mixture comprises anelastomeric polymeric mixture. Item 116. The cured elastomeric mixtureaccording to any one of items 100-115, wherein the crosslinkedpolyfunctionalized diene polymer has a Mc of about 500 to about 150,000grams/mole.

Item 300. A process for producing a cured polymeric product, comprisingproviding an additive manufacturing device comprising a source ofactinic radiation, an exterior support structure, an interior tankcapable of containing a liquid mixture, and an interior supportstructure; providing a liquid mixture comprising the actinic radiationcurable polymeric mixture of any one of items 1-30 to the interior tank;repeatedly forming upon a support structure a layer from the liquidmixture; using actinic radiation to cure each layer; thereby producing acured polymeric product. Item 301. The process of item 300, wherein eachlayer has a thickness of about 0.01 mm to about 1 mm. Item 302. Theprocess of item 300 or item 301, wherein the forming comprisessolidifying each layer by using the actinic radiation to trace a patternin the liquid material. Item 303. The process of item 300 or item 301,wherein the forming comprises dispensing the mixture from a printinghead having a set of nozzles. Item 304. The process of any one of items300-303, wherein the actinic radiation comprises UV or Visible light.Item 305. The process of any one of items 300-303, wherein the actinicradiation comprises light having a wavelength of about 320 to less than500 nm. Item 306. The process of any one of items 300-305, wherein theinterior tank is capable of receiving a liquid mixture from at least onecartridge. Item 307. The process of item 306, wherein the liquid mixtureis provided in at least one cartridge. Item 308. The process of item 306or 307, wherein at least two cartridges are utilized with one cartridgecomprising (a) and (b) and a second cartridge comprising (b) incombination with (c). Item 309. A kit for producing an elastomeric curedproduct by additive printing, the kit comprising at least twocartridges, wherein at least one cartridge comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and a chain extender based upon F or reactive with F; and atleast a second cartridge comprises a chain extender based upon F orreactive with F, at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer; and optionally a crosslinkerreactive with F. Item 310. The kit according to item 309, wherein atleast one of the first or second cartridge further comprises at leastone metal or metal oxide filler.

Item 400. A tire comprising at least one component comprised of thecured polymeric mixture according to any one of items 100-116. Item 401.A tire comprising at least one component comprised of the actinicradiation curable polymeric mixture of any one of items 1-30 that hasbeen cured. Item 402. The tire according to item 400 or item 401,wherein the at least one component is selected from a tread, a bead, asidewall, an innerliner, and a subtread. Item 403. The tire according toany one of items 400-402, wherein the at least one component comprises atread. Item 404. The tire according to item 403, wherein the treadcomprises: at least one of the following: a closed hollow void, anundercut void, and an overhung tread.

Item 501. A rubber good comprising the cured polymeric mixture accordingto any one of items 100-116. Item 501. A rubber good comprising theactinic radiation curable polymeric mixture of any one of items 1-30that has been cured. Item 502. The rubber good according to item 500 oritem 501, wherein the rubber good comprises a bushing, a seal, a gasket,a conveyor belt, a hose, or a glove.

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” Furthermore, to the extent the term“connect” is used in the specification or claims, it is intended to meannot only “directly connected to,” but also “indirectly connected to”such as connected through another component or components.

While the present application has been illustrated by the description ofembodiments thereof, and while the embodiments have been described inconsiderable detail, it is not the intention of the applicant torestrict or in any way limit the scope of the appended claims to suchdetail. Additional advantages and modifications will readily appear tothose skilled in the art. Therefore, the application, in its broaderaspects, is not limited to the specific details and embodimentsdescribed. Accordingly, departures may be made from such details withoutdeparting from the spirit or scope of the applicant's general inventiveconcept.

This application discloses several numerical range limitations thatsupport any range within the disclosed numerical ranges even though aprecise range limitation is not stated verbatim in the specificationbecause the embodiments could be practiced throughout the disclosednumerical ranges. With respect to the use of substantially any pluraland/or singular terms herein, those having skill in the art cantranslate from the plural to the singular and/or from the singular tothe plural as is appropriate to the context and/or application. Thevarious singular/plural permutations may be expressly set forth hereinfor sake of clarity. As well, all numerical limitations and ranges thatare preceded by the word “about” should be understood to include theparticular number or range without the about as if fully set forthherein.

1-26. (canceled)
 27. An additive manufacturing process for producing acured polymeric product in the form of a tire tread, comprisingproviding an additive manufacturing device comprising a source ofactinic radiation, an exterior support structure, an interior tankcapable of containing a liquid mixture, and an interior supportstructure, providing a liquid mixture comprising an actinic radiationcurable polymeric mixture comprising: (a) a polyfunctionalized dienemonomer-containing polymer (i) having monomers selected from at leastone of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene,and substituted derivatives of each of the foregoing, (ii) meeting atleast one of the following: having a Mn of about 3,000 to about 135,000grams/mole (polystyrene standard) or a Tg of about −105 to about −10°C., (iii) and having the formula: [P][F]_(n) where P represents a dienepolymer chain, F represents a functional group comprising cyanoacrylate,epoxide, aziridine, or thioepoxide, n is 2 to about 15, and each F canbe the same or different; (b) optionally a chain extender based upon For reactive with F; (c) at least one actinic radiation sensitive; (d)optionally, a photosensitizer; and (e) a polyfunctional crosslinkerreactive with F to the interior tank, repeatedly forming upon a supportstructure a layer from the liquid mixture, and using actinic radiationto cure each layer, thereby producing the cured polymeric product in theform of a tire tread, wherein at least one of the following is met: (ai)the polyfunctionalized diene monomer-containing polymer (a) is presentin an amount of 1-100 parts and (b) is present in an amount of 0-99parts; (aii) the at least one actinic sensitive photoinitiator (c) ispresent in an amount of about 1 part to about 10 parts (per 100 totalparts of (a) and (b)); or (aiii) the photosensitizer (d) is present inan amount of about 0.1 parts to about 5 parts (per 100 total parts of(a) and (b)).
 28. The process of claim 27, wherein the at least oneactinic radiation sensitive photoinitiator comprises at least one of: abenzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromaticα-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, abis-acylphosphinoxide, and a tris-acylphosphinoxide.
 29. The process ofclaim 27, wherein the polyfunctional crosslinker (e) is selected fromthe group consisting of polyol (meth)acrylates prepared from analiphatic diol, triol, or tetraol containing 2-100 carbon atoms;polyallylic compounds prepared from an aliphatic diol, triol or tetraolcontaining 2-100 carbon atoms; polyfunctional amines; or combinationsthereof.
 30. The process of claim 28, wherein the polyfunctionalcrosslinker (e) is selected from the group consisting of polyol(meth)acrylates prepared from an aliphatic diol, triol, or tetraolcontaining 2-100 carbon atoms; polyallylic compounds prepared from analiphatic diol, triol or tetraol containing 2-100 carbon atoms;polyfunctional amines; or combinations thereof.
 31. The process of claim27 wherein at least one of the following is met: (i) each layer has athickness of about 0.01 mm to about 1 mm; (ii) the forming comprisessolidifying each layer by using the actinic radiation to trace a patternin the liquid material; (iii) the forming comprises dispensing themixture from a printing head having a set of nozzles; (iv) the formingcomprises using the actinic radiation to provide at least one pattern onthe liquid material; (v) the forming comprises using the actinicradiation to project at least one image on the liquid material; (vi) theactinic radiation comprises UV or Visible light; (vii) the actinicradiation comprises light having a wavelength of about 320 to less than500 nm; (viii) the interior tank is capable of receiving a liquidmixture from at least one cartridge; (ix) the liquid material isprovided in at least one cartridge; or (x) at least two cartridges areutilized with one cartridge comprising (a) and (b) and a secondcartridge comprising (b) in combination with (c).
 32. The process ofclaim 31, wherein (i), at least one of (ii)-(v), at least one of (vi) or(vii), and at least one of (viii)-(x) are met.
 33. The process of claim27, wherein the actinic radiation curable polymeric mixture has a totalamount of (a) and (b) of 100 parts and (c) is present in a total amountof at least about 0.1 parts based upon 100 parts of (a) and (b).
 34. Theprocess of claim 27, wherein (ai) and at least one of (aii) and (aiii)are met.
 35. The process of claim 27, wherein the diene polymer chainfurther comprises at least one vinyl aromatic monomer.
 36. The processof claim 27, wherein the polyfunctional crosslinker (e) is selected fromat least one of: Trimethylolpropane tri(meth)acrylate, Pentaerythritoltetraacrylate, Pentaerythritol triacrylate, Trimethylolpropaneethoxylate triacrylate, Acrylated epoxidized soybean oil, DitrimethylolPropane Tetraacrylate, Di-pentaerythritol Polyacrylate,Di-pentaerythritol Polymethacrylate, Di-pentaerythritol triacrylate,Di-pentaerythritol trimethacrylate, Di-pentaerythritol tetracrylate,Di-pentaerythritol tetramethacrylate, Di-pentaerythritolpent(meth)acrylate, Di-pentaerythritol hexa(meth)acrylate,Pentaerythritol Poly(meth)acrylate, Pentaerythritol tri(meth)acrylate,Pentaerythritol tetra(meth)acrylate, Pentaerythritolpenta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylatedglycerine triacrylate, ϵ-Caprolactone ethoxylated isocyanuric acidtriacrylate and Ethoxylated isocyanuric acid triacrylate,Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate,ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycoldi(meth)acrylate, ethyleneglycol dimethacrylate (EDMA),polyethyleneglycol di(meth)acrylates, polypropyleneglycoldi(meth)acrylates, polybutyleneglycol di(meth)acrylates,2,2-bis(4-(meth)acryloxyethoxyphenyl) propane,2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane)tetra(meth)acrylate, and combinations thereof.
 37. The process of claim27, wherein the chain extender (b) is present and comprises an(meth)acrylate monomer selected from C2 to about C18 alkylfunctionalized (meth)acrylates.
 38. The process of claim 27, wherein thechain extender has a Tg of about −65 to about 10° C. and the chainextender has a Mw of about 72.06 to about 135,000 grams/mole.
 39. Theprocess of claim 55, wherein the photosensitizer (d) is present andcomprises at least one of a ketocoumarin, a xanthone, a thioxanthone, apolycyclic aromatic hydrocarbon, and an oximester derived from aromaticketone.
 40. The process of claim 27, wherein the photoinitiator (c)comprises a benzophenone.
 41. The process of claim 27, wherein thephotoinitiator (c) comprises an aromatic α-hydroxyketone, a benzilketal,or an aromatic α-aminoketone.
 42. The process of claim 27, wherein theactinic radiation curable polymeric mixture further comprises at leastone filler.
 43. The process of claim 42, wherein at least one of thefollowing is met: a. the at least one filler is present in an amount ofup to about ⅔ of the total volume of the actinic radiation curablepolymeric mixture; or b. the at least one filler is present in an amountof about 40 to about 80 parts (based upon 100 total parts of (a) and(b)).
 44. The process of claim 27, wherein the actinic radiation curablepolymeric mixture has a viscosity at 25° C. of about 100 to about 5,000cps.
 45. An additive manufacturing process for producing a curedpolymeric product in the form of a tire tread, comprising providing anadditive manufacturing device comprising a source of actinic radiation,an exterior support structure, an interior tank capable of containing aliquid mixture, and an interior support structure, providing a liquidmixture comprising an actinic radiation curable polymeric mixturecomprising: (a) a polyfunctionalized diene monomer-containing polymercomprising 1,3-butadiene monomers, (ii) meeting at least one of thefollowing: having a Mn of about 3,000 to about 135,000 grams/mole(polystyrene standard) or a Tg of about −105 to about −10° C., (iii) andhaving the formula: [P][F]_(n) where P represents a diene polymer chain,F represents a functional group comprising cyanoacrylate, epoxide,aziridine, or thioepoxide, n is 2 to about 15, and each F can be thesame or different; (b) optionally a chain extender based upon F orreactive with F; (c) at least one actinic radiation sensitivephotoinitiator selected from the group consisting of a benzophenone, anaromatic α-hydroxyketone, a benzilketal, an aromatic α-aminoketone, aphenylglyoxalic acid ester, a mono-acylphosphinoxide, abis-acylphosphinoxide, and a tris-acylphosphinoxide, and combinationsthereof; (d) optionally, a photosensitizer; and (e) a polyfunctionalcrosslinker reactive with F and selected from the group consisting ofpolyol (meth)acrylates prepared from an aliphatic diol, triol, ortetraol containing 2-100 carbon atoms; polyallylic compounds preparedfrom an aliphatic diol, triol or tetraol containing 2-100 carbon atoms;polyfunctional amines; or combinations thereof to the interior tank,repeatedly forming upon a support structure a layer from the liquidmixture, and using actinic radiation to cure each layer, therebyproducing the cured polymeric product in the form of a tire tread,wherein at least one of the following is met: (ai) thepolyfunctionalized diene monomer-containing polymer (a) is present in anamount of 1-100 parts and (b) is present in an amount of 0-99 parts;(aii) the at least one actinic sensitive photoinitiator (c) is presentin an amount of about 1 part to about 10 parts (per 100 total parts of(a) and (b)); or (aiii) the photosensitizer (d) is present in an amountof about 0.1 parts to about 5 parts (per 100 total parts of (a) and(b)).
 46. The process of claim 45, wherein the diene polymer chainfurther comprises at least one vinyl aromatic monomer.
 47. The processof claim 45, wherein the cured polymeric product in the form of a tiretread has crosslinkages that are essentially free of sulfur.
 48. Theprocess of claim 27, wherein the cured polymeric product in the form ofa tire tread has crosslinkages that are essentially free of sulfur. 49.The process of claim 27, wherein the cured polymeric product in the formof a tread comprises at least one of the following: a closed hollowvoid, an undercut void, or an overhung void.
 50. The process of claim45, wherein the cured polymeric product in the form of a tread comprisesat least one of the following: a closed hollow void, an undercut void,or an overhung void.